Print head pulsing techniques for multicolor printers

ABSTRACT

In one aspect of the invention there is disclosed a multicolor thermal imaging system wherein different heating elements on a thermal print head can print on different color-forming layers of a multicolor thermal imaging member in a single pass. The line-printing time is divided into segments, each of which is divided into a plurality of subintervals. All of the pulses within the segments have the same energy. In one embodiment, every pulse has the same amplitude and duration. Different colors are selected for printing during the different segments by varying the fraction of subintervals that contain pulses. This technique allows multiple colors to be printed using a thermal print head with a single strobe signal line. Pulsing patterns may be chosen to reduce the coincidence of pulses provided to multiple print head elements, thereby reducing the peak power requirements of the print head.

REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of, and claims the benefit ofpriority of, co-pending U.S. patent application Ser. No. 11/397,251,filed on Apr. 3, 2006, which is a Continuation of U.S. patentapplication Ser. No. 10/806,749, filed on Mar. 23, 2004, now U.S. Pat.No. 7,166,558, which is a Division of U.S. patent application Ser. No.10/151,432, filed on May 20, 2002, now U.S. Pat. No. 6,801,233, whichclaims priority from Provisional Application Ser. Nos. 60/364,198, filedon Mar. 13, 2002, and 60/294,486, filed on May 30, 2001. Thisapplication is also a continuation-in-part of, and claims the benefit ofpriority of, co-pending U.S. patent application Ser. Nos. 11/159,880,filed on Jun. 23, 2005, and 10/374,847, filed on Feb. 25, 2003. Thecontents of those patent applications are incorporated herein byreference.

This application is related to the following commonly assigned, UnitedStates patent applications and patents, the entire disclosures of whichare hereby incorporated by reference herein in their entirety:

U.S. Pat. No. 6,951,952 B2 which describes and claims color-formingcompositions for use in the present invention;

U.S. Pat. No. 7,008,759 B2 which describes and claims color-formingcompositions for use in the present invention;

U.S. Pat. No. 7,176,161 B2 which describes and claims color-formingcompositions for use in the present invention;

U.S. Pat. No. 7,279,264 B2 which describes and claims color-formingcompositions for use in the present invention;

U.S. patent application Ser. No. 10/374,847, filed Feb. 25, 2003 whichdescribes and claims methods for image stitching for use in the presentinvention;

U.S. Pat. No. 7,282,317 B2 which describes and claims color-formingcompositions for use in the present invention;

U.S. patent application Ser. No. 11/159,880, filed Jun. 23, 2005,entitled “Print Head Pulsing Techniques for Multicolor Printers”;

U.S. patent application Ser. No. 11/400,734, filed Apr. 6, 2006, whichdescribes and claims an imaging method for use in the present invention;and

U.S. patent application Ser. No. 11/400,735, filed Apr. 6, 2006, whichdescribes and claims an imaging method for use in the present invention;and

U.S. patent application Ser. No. 10/910,880, filed Aug. 4, 2004, whichdescribes and claims a thermal response correction system for use in thepresent invention; and

U.S. patent application Ser. No. 10/990,672, filed Jan. 10, 2005, whichdescribes and claims a method for controlling the uniformity of printdensity of a thermal print head array.

FIELD OF THE INVENTION

The present invention relates generally to a thermal imaging system and,more particularly, to a multicolor thermal imaging system wherein atleast two image-forming layers of a thermal imaging member are addressedat least partially independently by a single thermal printhead or bymultiple printheads from the same surface of the thermal imaging member.

BACKGROUND OF THE INVENTION

Conventional methods for color thermal imaging such as thermal waxtransfer printing and dye-diffusion thermal transfer typically involvethe use of separate donor and receiver materials. The donor materialtypically has a colored image-forming material, or a color-formingimaging material, coated on a surface of a substrate and theimage-forming material or the color-forming imaging material istransferred thermally to the receiver material. In order to makemulticolor images, a donor material with successive patches ofdifferently-colored, or different color-forming, material may be used.In the case of printers having either interchangeable cassettes or morethan one thermal head, different monochrome donor ribbons are utilizedand multiple color separations are made and deposited successively aboveone another. The use of donor members with multiple different colorpatches or the use of multiple donor members increases the complexityand the cost of such printing systems. It would be simpler to have asingle-sheet imaging member that has the entire multicolor imagingreagent system embodied therein.

There have been described in the prior art numerous attempts to achievemulticolor, direct thermal printing. For example, there are knowntwo-color direct thermal systems in which formation of the first coloris affected by formation of the second color. U.S. Pat. No. 3,895,173describes a dichromatic thermal recording paper which includes two leucodye systems, one of which requires a higher activation temperature thanthe other. The higher temperature leuco dye system cannot be activatedwithout activating the lower temperature leuco dye system. There areknown direct thermal imaging systems that utilize an imaging memberhaving two color-forming layers coated on opposite surfaces of atransparent substrate. The imaging member is addressed by multipleprintheads independently from each side of the imaging member. A thermalimaging system of this type is described in U.S. Pat. No. 4,956,251.

Thermal systems that exploit a combination of dye transfer imaging anddirect thermal imaging are also known. In systems of this type, a donorelement and a receiver element are in contact with one another. Thereceiver element is capable of accepting dye, which is transferred fromthe donor element, and also includes a direct thermal color-forminglayer. Following a first pass by a thermal printhead during which dye istransferred from the donor element to the receiver element, the donorelement is separated from the receiver and the receiver element isimaged a second time by a printhead to activate the direct thermalimaging material. This type of thermal system is described in U.S. Pat.No. 4,328,977. U.S. Pat. No. 5,284,816 describes a thermal imagingmember that comprises a substrate having a direct thermal color-forminglayer on one side and a receiver element for dye transfer on the otherside.

There are also known thermal imaging systems that utilize imagingmembers having spatially separated regions comprising direct thermalcolor-forming compositions that form different colors. U.S. Pat. Nos.5,618,063 and 5,644,352 describe thermal imaging systems in whichdifferent areas of a substrate are coated with formulations for formingtwo different colors. A similar bicolored material is described in U.S.Pat. No. 4,627,641.

Another known thermal imaging system is a leuco-dye-containing, directthermal system in which information is created by activating the imagingmaterial at one temperature and erased by heating the material to adifferent temperature. U.S. Pat. No. 5,663,115 describes a system inwhich a transition from a crystalline to an amorphous, or glass, phaseis exploited to give a reversible color formation. Heating the imagingmember to the melting point of a steroidal developer results in theformation of a colored amorphous phase while heating of this coloredamorphous phase to a temperature lower than the crystalline meltingpoint of the material causes recrystallization of the developer anderasure of the image.

There is also known a thermal system containing one decolorizable, leucodye containing, color-forming layer and a second leuco dye containinglayer capable of forming a different color. The first color-forminglayer colorizes at a low temperature while the second layer colorizes ata higher temperature, at which temperature the decolorization of thefirst layer also takes place. In such systems, either one or the othercolor can be addressed at a particular point. U.S. Pat. No. 4,020,232discloses formation of one color by a leuco dye/base mechanism and theother by a leuco dye/acid mechanism wherein the color formed by onemechanism is neutralized by the reagent used to form the other.Variations of this type of system are described in U.S. Pat. Nos.4,620,204; 5,710,094; 5,876,898 and 5,885,926.

Direct thermal imaging systems are known in which more than one layermay be addressed independently, and in which the most sensitivecolor-forming layer overlies the other color-forming layers. Followingformation of an image in the layer outermost from the film base, thelayer is deactivated by exposure to light prior to forming images in theother, less sensitive, color-forming layers. Systems of this type aredescribed in U.S. Pat. Nos. 4,250,511; 4,734,704; 4,833,488; 4,840,933;4,965,166; 5,055,373; 5,729,274; and 5,916,680.

As the state of the thermal imaging art advances and efforts are made toprovide new thermal imaging systems that can meet new performancerequirements, and to reduce or eliminate some of the undesirablerequirements of the known systems, it would be advantageous to have amuticolor thermal imaging system in which at least two differentimage-forming layers of a single imaging member can be addressed atleast partially independently from the same surface by a single thermalprinthead or by multiple thermal printheads so that each color can beprinted alone or in selectable proportion with the other color(s).

SUMMARY OF THE INVENTION

It is therefore an object of this invention to provide a multicolorthermal imaging system which allows for addressing, at least partiallyindependently, with a single thermal printhead or multiple thermalprintheads, at least two different image-forming layers of an imagingmember from the same surface of the imaging member.

Another object of the invention is to provide such a multicolor thermalimaging system wherein each color can be printed alone or in selectableproportion with the other color(s).

Yet another object of the invention is to provide a multicolor thermalimaging system wherein at least two different image-forming layers of animaging member are addressed at least partially independently bycontrolling the temperature applied to each of the layers and the timeeach of the layers is subjected to such temperature.

Still another object of the invention is to provide a multicolor thermalimaging system wherein at least two different image-forming layers of animaging member are addressed at least partially independently with athermal printhead or multiple thermal printheads from the same surfaceof the imaging member and one or more image-forming layers are addressedwith a thermal printhead or multiple thermal printheads from theopposing surface of the imaging member.

A further object of the invention is to provide a multicolor thermalimaging system wherein at least two different image-forming layers of animaging member are addressed at least partially independently with asingle pass of a thermal printhead.

Another object of the invention is to provide a multicolor thermalimaging system which is capable of providing images which have adequatecolor separation for a particular application in which the system isused.

Still another object of the invention is to provide novel thermalimaging members.

These and other objects and advantages are accomplished in accordancewith the invention by providing a multicolor thermal imaging systemwherein at least two, and preferably three, image-forming layers of athermal imaging member can be addressed at least partiallyindependently, from the same surface of the imaging member, by a singlethermal printhead or by multiple thermal printheads. The advantageousthermal imaging system of the invention is based upon at least partiallyindependently addressing a plurality of image-forming layers of athermal imaging member utilizing two adjustable parameters, namelytemperature and time. These parameters are adjusted in accordance withthe invention to obtain the desired results in any particular instanceby selecting the temperature of the thermal printhead and the period oftime for which thermal energy is applied to each of the image-forminglayers. According to the invention, each color of the multicolor imagingmember can be printed alone or in selectable proportion with the othercolor(s). Thus, as will be described in detail, according to theinvention the temperature-time domain is divided into regionscorresponding to the different colors it is desired to combine in afinal print.

The image-forming layers of the thermal imaging member undergo a changein color to provide the desired image in the imaging member. The changein color may be from colorless to a color or from colored to colorlessor from one color to another color. The term “image-forming layer” asused throughout the application including in the claims, includes allsuch embodiments. In the case where the change in color is fromcolorless to a color, an image having different levels of opticaldensity (i.e., different “gray levels”) of that color may be obtained byvarying the amount of color in each pixel of the image from a minimumdensity, Dmin, which is substantially colorless, to a maximum density,Dmax, in which the maximum amount of color is formed. In the case wherethe change in color is from colored to colorless, different gray levelsare obtained by reducing the amount of color in a given pixel from Dmaxto Dmin, where ideally Dmin is substantially colorless. In this case,formation of the image involves converting a given pixel from a coloredto a less colored, but not necessarily, colorless state.

A number of techniques can be used to achieve the advantageous resultsprovided by exploiting the time and temperature variables in accordancewith the invention. These include thermal diffusion with buried layers,chemical diffusion or dissolution in conjunction with timing layers,melting transitions and chemical thresholds. Each of these techniquesmay be utilized alone, or in combination with others, to adjust theregions of the imaging member in which each desired color will beformed.

In a preferred embodiment, a thermal imaging member includes two, andpreferably three, different image-forming layers carried by the samesurface of a substrate. In another preferred embodiment, a thermalimaging member includes a layer or layers of image-forming materialcarried by one surface of a substrate and a layer or layers ofimage-forming material carried by the opposing surface of the substrate.According to the imaging system of the invention, the image-forminglayers of the imaging member can be addressed at least partiallyindependently by a single thermal printhead or multiple printheads incontact with the same surface of the imaging member. In a preferredembodiment, one or two thermal printheads can be utilized to address atleast partially independently from one surface of the imaging member twodifferent image-forming layers carried by one surface of the substrateand another thermal printhead utilized to address at least partiallyindependently from the opposing surface of the imaging member one ormore image-forming layers carried by the opposing surface of thesubstrate. The thermal printheads which contact the opposing surfaces ofthe imaging member can be arranged directly opposite one another oroffset from one another such that there is a delay between the timesthat any discrete area of the imaging member comes into contact with therespective thermal printheads.

In another preferred embodiment one thermal printhead may be used toaddress at least partially independently two or more differentimage-forming layers of the imaging member in a single pass and,optionally, a second thermal printhead used to address one or moreimage-forming layers, either in conjunction with the first thermalprinthead, or subsequent thereto.

In one aspect of the invention there is disclosed a multicolor thermalimaging system wherein different heating elements on a thermal printhead can print on at least three different color-forming layers of amulticolor thermal imaging member in a single pass. The line-printingtime is divided into segments, each of which is divided into a pluralityof subintervals. All of the pulses within the segments have the sameenergy. In one embodiment, every pulse has the same amplitude andduration. Different colors are selected for printing during thedifferent segments by varying the fraction of subintervals that containpulses. This technique allows multiple colors to be printed using athermal print head with a single strobe signal line. Pulsing patternsmay be chosen to reduce the coincidence of pulses provided to multipleprint head elements, thereby reducing the peak power requirements of theprint head.

Other features and advantages of various aspects and embodiments of thepresent invention will become apparent from the following descriptionand from the claims.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the invention as well as other objects andadvantages and further features thereof, reference is made to thefollowing detailed description of various preferred embodiments thereoftaken in conjunction with the accompanying drawings wherein:

FIG. 1 is a graphical representation of the colors which may be printedby a prior art two-color, direct thermal printing system;

FIG. 2 is a graphical representation of the colors which may be printedby a two-color direct thermal printing embodiment of the invention;

FIG. 3 is a graphical illustration of non-independent colored-dotformation encountered in prior art direct thermal printing;

FIG. 4 is a graphical representation of the colors which may be printedby a prior art three-color direct thermal printing system and by athree-color direct thermal printing embodiment of the invention;

FIG. 5 is a graphical representation illustrating one embodiment of theinvention;

FIG. 6 is a graphical representation further illustrating the embodimentof the invention illustrated in FIG. 5;

FIG. 7 is a graphical representation illustrating the practice of athree-color embodiment of the invention;

FIG. 8 is a partially schematic, side sectional view of a two colorimaging member according to the invention which utilizes thermal delays;

FIG. 9 is a partially schematic, side sectional view of a three colorimaging member according to the invention which utilizes thermal delays;

FIG. 10 is a partially schematic, side sectional view of another threecolor imaging member according to the invention which utilizes thermaldelays;

FIG. 11 is a partially schematic, side sectional view of a thermalprinting apparatus for carrying out an embodiment of the invention;

FIG. 12 is a graphical representation of a method for applying voltageto a conventional thermal printhead during a prior art thermal imagingmethod;

FIG. 13 is a graphical representation of a method for applying voltageto a conventional thermal printhead in the practice of an embodiment ofthe thermal imaging system of the invention;

FIG. 14 is a graphical representation of another method for applyingvoltage to a conventional thermal printhead in the practice of anembodiment of the thermal imaging system of the invention;

FIG. 15 is a graphical representation showing the development time oftwo dyes as a function of temperature;

FIG. 16 is a partially schematic, side sectional view of a multicolorimaging member according to the invention which utilizes chemicaldiffusion and dissolution;

FIG. 17 is a partially schematic, side sectional view of anegative-working multicolor imaging member according to the invention;and

FIG. 18 is a partially schematic, side sectional view of a three colorimaging member according to the invention which utilizes chemicaldiffusion and dissolution.

FIG. 19 is a partially schematic, side sectional view of a three-colorthermal imaging member according to the invention;

FIG. 20 is a partially schematic, side sectional view of a thermalprinting head addressing a thermal imaging member according to theinvention;

FIG. 21 is a partially schematic, plan view of some thermal heatingelements of a thermal printing head according to the invention;

FIG. 22 is a graph that shows the voltage across a print head elementover time in a printer in which the line time is divided into aplurality of subintervals;

FIG. 23 is a graph that shows the voltage across a print head elementover time in a printer in which the line time is divided into threesegments, each of which is divided into a plurality of subintervals;

FIG. 24 is a graph that shows the voltage across a print head elementover time in a printer in which the line time is divided into threesegments, and in which pulses of the same length are provided in eachsegment according to one embodiment of the present invention;

FIG. 25 is a flowchart of a method that is performed by a printer toselect a pattern of pulses to provide to a print head element to selecta particular color to print according to one embodiment of the presentinvention;

FIG. 26 is a graph that shows the temporal allocation of three segmentsof a line printing time for four successive print head elementsaccording to an embodiment of the present invention;

FIG. 27 is a graph that shows the temporal allocation of three segmentsof a line printing time for four successive print head elements in acase of compromised load leveling;

FIG. 28 is a graph that shows the temporal allocation of three segmentsof a line printing time for four successive print head elementsaccording to an embodiment of the present invention;

FIG. 29 is a graph that shows the temporal allocation of three segmentsof a line printing time for four successive print head elements forprinting a combination of high- and low-power colors according to anembodiment of the present invention;

FIG. 30 is a graph that shows the voltage across a print head elementover time in a printer in which the line time is divided into threesegments, and in which pulses of the same length are provided in eachsegment according to a preferred embodiment of the present invention;and

FIG. 31 is a block diagram of an image processing and pulse generationportion of a printing system of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

As previously mentioned, according to the multicolor thermal imagingsystem of the invention, two or more image-forming layers of amulticolor thermal imaging member are addressed at least partiallyindependently from the same surface of the imaging member, so that eachcolor may be printed alone or in selectable proportion with the others,and these results are accomplished by selecting the colors on the basisof two adjustable parameters, namely temperature and time. Thetemperature-time domain is divided into regions corresponding to thedifferent colors it is desired to combine.

To assist those skilled in the art to better understand the concept ofindependent control of color, as applied to multicolor direct thermalprinting according to the present invention, it is helpful to considerfirst a prior art thermal imaging system involving a thermal imagingmember containing two color-forming layers on a white reflectivesubstrate. For the purpose of discussion it will be considered that onelayer is a cyan color-forming layer and the other a magentacolor-forming layer and, further, that the cyan layer has a temperaturethreshold above that of the magenta layer. If a fixed-length thermalpulse is applied to a discrete point, or area, on this imaging member, acolor will form depending upon the magnitude of the pulse. Pulses ofincreasing magnitude lead to increasing peak temperature in theimage-forming layers at the location of the thermal pulse. Theoriginally white medium will become progressively more magenta as themagenta threshold temperature for coloration is exceeded and thenprogressively more blue, i.e., magenta plus cyan, as the cyan thresholdtemperature for coloration is exceeded. This progression of color may berepresented by the two-dimensional color diagram illustrated in FIG. 1.

As shown by the curvilinear path, the color first moves in the magentadirection as the threshold temperature is exceeded in the magenta layerand then in the cyan direction, i.e., towards blue, as the thresholdtemperature is surpassed in the cyan layer. Each point on the color pathis associated with the magnitude of the thermal pulse that created itand there is a fixed ratio of magenta and cyan color associated witheach pulse magnitude. A similar progression of colors is produced if theapplied pulse has a fixed magnitude and variable duration provided thatthe power is sufficient ultimately to raise both dye layers above theirthreshold coloration temperatures. In this case, when the pulse begins,the two dye layers will advance in temperature. For longer and longerpulse durations the dye temperatures will first exceed the magentathreshold and then the cyan threshold. Each pulse duration willcorrespond to a well-defined color, again passing from white to magentato blue along a curvilinear path. Prior art thermal imaging systems,using either a modulation of pulse amplitude or pulse duration, aretherefore essentially limited to the reproduction of colors falling oncurvilinear paths in the color space.

The present invention, by addressing at least partially independentlythe different image-forming layers of a multicolor thermal imagingmember, provides a thermal imaging method in which the colors formed arenot constrained by a one dimensional path but can instead be selectedthroughout regions on both sides of the path as is illustrated in theshaded region of FIG. 2.

In the foregoing description the term “partially independently” is usedto describe the addressing of the image-forming layers. The degree towhich the image-forming layers can be addressed independently is relatedto the image property commonly referred to as “color separation”. Asstated previously, an object of the invention is to provide images withadequate color separation for the various applications for which thepresent thermal imaging method is suitable. For example, photographicimaging requires that the color separation be comparable to that whichcan be obtained with conventional photographic exposure and development.Depending upon the printing time, available printing power, and otherfactors, various degrees of independence in the addressing of theimage-forming layers can be achieved. The term “independently” shall beused to refer to instances in which the printing of one color-forminglayer typically results in a very small, but not generally visibleoptical density (density <0.05) in the other color-forming layer(s). Inthe same manner, the term “substantially independent” color printingwill be used to refer to instances in which inadvertent or unintentionalcoloration of another image-forming layer or layers results in a visibledensity which is at a level typical of interimage coloration inmulticolor photography (density <0.2). In some instances color crosstalkat this level is considered photographically desirable. The term“partially independent” addressing of the image-forming layers is usedto refer to instances in which the printing of maximum density in thelayer being addressed results in the coloration of another image-forminglayer or layers at a density higher than 0.2 but not higher than about1.0. The phrase “at least partially independently” is inclusive of allof the degrees of independence described above.

A distinction between the thermal imaging system of the invention andthe prior art thermal imaging methods can be seen from the nature of theimages which are obtainable from each. When two image-forming layers arenot addressable independently one or both of them will not be able to beprinted without substantial color contamination from the other. Forexample, consider a single-sheet thermal imaging member which isdesigned to provide two colors, Color 1 and Color 2, with temperaturethresholds for coloration of, respectively, T₁ and T₂ where T₁>T₂.Consider the attempt to form a dot of a single color using a heatingelement to heat the thermal member from the top surface. There will be apoint, typically in the center of the heated area, where the temperatureT takes its highest value, T_(max). Away from this point T is lower,falling off quickly outside of the heated area to a temperature wellbelow T₁ or T₂, as indicated schematically in FIG. 3 a. A “clean” dot ofColor 2 may be printed in regions where the local temperature T isgreater than T₂ but less than T₁ (see FIG. 3 b). If T_(max) exceeds T₁,then the dot will be contaminated with Color 1 in the center andindependent color formation will no longer be possible.

It is notable that an attempt to print a dot of Color 1 will requirethat T_(max)>T₁, and since T₁>T₂ this will inevitably mean that Color 2will be printed as well (see FIG. 3 c). Consequently, independentprinting of Color 1 is not possible. An attempt can be made to correctthis problem by incorporating a bleaching of Color 2 which occurswhenever Color 1 is formed. If bleaching is carried out, only Color 1will be visible in the heated region where T is greater than T₁.However, this does not constitute independent addressing for tworeasons. First, it is not possible to obtain arbitrary mixtures of Color1 and Color 2 in this manner. Second, there remains an annular regionaround each dot of Color 1 within which Color 2 is not bleached (seeFIG. 3 d).

According to the present invention, independent addressing of bothcolors in the above example is achieved by introducing a timingmechanism by which the coloration of the second dye layer is delayedwith respect to the coloration of the first dye layer. During this delayperiod, it is possible to write on the first dye layer withoutcolorizing the second; and, if the second layer has a lower thresholdtemperature for coloration than the first, it will later be possible towrite on the second without exceeding the threshold of the first.

In one embodiment, the method of the invention will allow completelyindependent formation of cyan or magenta. Thus, in this embodiment, onecombination of temperature and time will permit the selection of anydensity of magenta on the white-magenta axis while not producing anynoticeable cyan color. Another combination of temperature and time willpermit the selection of any density of cyan on the white-cyan axis whilenot producing any noticeable magenta coloration. A juxtaposition of twotemperature-time combinations will allow the selection of anycyan/magenta mixture within the enclosed area indicated on FIG. 2, thusproviding independent control of cyan and magenta.

In other embodiments of the invention, thermal addressing of theimage-forming layers, rather than being completely independent, can besubstantially independent or only partially independent. Variousconsiderations, including material properties, printing speed, energyconsumption, material costs and other system requirements may dictate asystem with increased color cross-talk. While independent orsubstantially independent color selection according to the invention isdesirable for photographic-quality printing, this requirement is of lessimportance in the printing of certain images such as, for example,product labels or multicolor coupons, and in these instances may besacrificed for economic considerations such as improved printing speedor lower costs.

In these embodiments of the invention where addressing of the separateimage-forming layers of a multicolor thermal imaging member is notcompletely, but rather substantially, or partially, independent, and bydesign the printing of cyan may produce a controlled amount of magentacolor formation and vice-versa, it will not be possible to printcompletely pure magenta or completely pure cyan. Indeed, there will be aregion of the color box near each coordinate axis that representsunprintable colors and the available colors will fall into a morerestricted region such as the shaded area illustrated schematically inFIG. 2. In these instances, although the palette of colors available isless than the selection encompassed by the embodiments of the inventionwhere color selection is controlled completely independently, it isnevertheless greatly superior to the very restricted selection of colorsallowed by the prior art systems.

Similar considerations apply to three-color embodiments of the presentinvention. For these embodiments, the color space is three-dimensionaland is commonly referred to as a “color cube” as is illustrated in FIG.4. If fixed-length thermal pulses of increasing temperature are appliedto a prior art multicolor direct thermal printing medium, it is possibleto produce colors which fall on a curvilinear path through the cube asillustrated by the dotted arrow. As seen, the path extends from onecolor, usually white, to another color, usually black, while passingthrough a fixed variety of colors. In comparison, one embodiment of thepresent invention advantageously provides the capability to print anycolor within the three-dimensional color cube. In other embodiments ofthe invention, where addressing of the color-forming layers issubstantially or partially independent, formation of colors within theshaded area of FIG. 4 is possible, again providing considerably moreflexibility in the choice of colors than that offered by prior artdirect thermal printing systems.

For the purpose of describing the temperature and time parameter featureof the invention, reference is made to FIG. 5 which is a graphicalrepresentation of one embodiment of the invention. For example, thethermal imaging member may contain a cyan image-forming material whichprovides a visible cyan color region, C, when subjected to a relativelyhigh temperature for a short period of time and a magenta image-formingmaterial which provides a visible magenta region, A, when subjected to alower temperature for a longer period of time. A combination of shortand long pulses of heat at different temperatures can be utilized toselect the proportions of each color. It can be seen that according tothe invention, since there are two adjustable variables involved and twoor more image-forming materials, at least substantially completeindependent control of any particular color according to the inventionrequires that each color be assigned a substantially unique range oftime and temperature.

Other considerations relevant to the multicolor thermal imaging systemof the invention can be understood from the following discussion of atwo-color leuco dye system in conjunction with FIG. 6. Consider, forexample, a system wherein color is generated by a leuco dye that isbeing thermally diffused to combine with an acid developer material. Inthis instance, it may not be possible to constrain the colorant responseto a completely enclosed region such as is shown in FIG. 5. Although itmay be intended to utilize temperatures and time periods within theregions shown in FIG. 5 the imaging member may also be responsive at awider range of temperatures and time periods. Referring now to FIG. 6 itcan be seen that in this illustrative example, regions A and C would bethe regions selected for printing magenta and cyan, respectively.However, the temperature and time combinations in regions B and E, forexample, will also be adequate to permit diffusion of the magenta leucodye to the developer. Also, cyan will be printed for temperature-timecombinations in regions D and E. Thus, in order to obtain substantiallycomplete independent control of cyan and magenta image-forming materialsaccording to the invention a magenta printing region, A, shouldpreferably be selected such that it does not overlap regions C, D or E,or any other region in which cyan is responsive. Conversely, cyanprinting region, C, should preferably be selected such that it does notoverlap regions A, B and E, or any other region in which magenta isresponsive. Generally, this means that for the illustrative diffusiveleuco dye system, the separately selected color printing regions shouldbe arranged along a slope decreasing from higher to lower time periodsand from lower to higher temperatures. It will be appreciated that inactual implementations, the chosen printing regions may not berectangular in shape as shown in the schematic representation, but willhave a shape governed by the behavior of the physical process that leadsto coloration, and may contain limited regional overlap consistent withthe desired color separation for a particular application.

A suitable schematic arrangement for a three-color diffusion-controlledleuco dye system according to the invention is illustrated in FIG. 7where the time-temperature combinations for printing magenta, cyan andyellow, respectively, are shown.

In preferred embodiments of the invention, the temperatures selected forthe color-forming regions generally are in the range of from about 50°C. to about 450° C. The time period for which the thermal energy isapplied to the color-forming layers of the imaging member is preferablyin the range of from about 0.01 to about 100 milliseconds.

As mentioned previously, a number of image-forming techniques may beexploited in accordance with the invention including thermal diffusionwith buried layers, chemical diffusion or dissolution in conjunctionwith timing layers, melting transitions and chemical thresholds.

Referring now to FIG. 8 there is seen a multicolor thermal imagingmember that utilizes thermal time delays to define the printing regionsfor the respective colors to be formed. The imaging member 10 reliesupon the diffusion of heat through the imaging member in order to obtainthe timing differences that are exploited according to the invention.Imaging member 10 includes a substrate 12 carrying cyan and magentaimage-forming layers, 14 and 16, respectively, and spacer interlayer 18.It should be noted here that in various embodiments of the invention theimage-forming layers may themselves comprise two or more separatelayers. For example, where the image-forming material is a leuco dyewhich is used in conjunction with a developer material, the leuco dyeand developer material may be disposed in separate layers.

Where the imaging member 10 is heated by a thermal printhead from abovecyan image-forming layer 14 the heat will penetrate into the imagingmember to reach magenta image-forming layer 16. Cyan image-forming layer14 will be heated above its coloration threshold temperature almostimmediately by the thermal printhead after the heat is applied, butthere will be a more significant delay before the magenta image-forminglayer 16 approaches its threshold temperature. If both image-forminglayers were such as to begin forming color at the same temperature,e.g., 120° C., and the printhead were to heat the surface of imagingmember 10 to a temperature of substantially more than 120° C., then thecyan image-forming layer 14 would begin to provide cyan color almost atonce whereas magenta image-forming layer 16 would begin to providemagenta color after a time delay dependent upon the thickness of spacerlayer 18. The chemical nature of the activation of the color in eachlayer would not be critical.

To provide multicolor printing in accordance with the invention eachimage-forming layer is arranged to be activated at a differenttemperature, e.g., T₅ for cyan image-forming layer 14 and T₆ for the“buried” magenta image-forming layer 16. This result can be achieved,for example, by arranging these image-forming layers to have differentmelting temperatures or by incorporating in them different thermalsolvents, which will melt at different temperatures and liquefy theimage-forming materials. Temperature T₅ is selected to be higher thanT₆.

Where a temperature less than T₆ is applied to the imaging member forany length of time no color will be formed. Thus, the imaging materialmay be shipped and stored safely at a temperature less than T₆. Where aprinting element in contact with layer 14 applies such heating as tocause a temperature between T₅ and T₆ to be attained by image-forminglayer 16, then the cyan image-forming layer 14 will remain substantiallycolorless and magenta image-forming layer 16 will develop magenta colordensity after a time delay which is a function of the thickness ofspacer layer 18. Where a temperature just above T₅ is applied to theimaging member by a printing element in contact with image-forming layer14, then the cyan image-forming layer 14 will begin developing colordensity immediately and magenta image-forming layer 16 will also developmagenta color density but only after a time delay. Said another way, atintermediate temperatures and relatively long time periods it ispossible to produce magenta color without cyan color and for hightemperatures and relatively short time periods, it is possible toproduce cyan color without any magenta color. A relatively short, hightemperature heat pulse juxtaposed with a longer, intermediatetemperature heat pulse will result in the combination of magenta andcyan colors in selected proportions.

It will be appreciated by those skilled in the art that the mechanismsdescribed above in reference to FIG. 8 will provide optimumdifferentiation between the two colors where the thermal printhead ischosen so as to conduct heat away efficiently from the surface ofimaging member 10 after the application of heat. This is particularlyimportant immediately following printing a pixel in image-forming layer14.

The image-forming layers 14 and 16 of imaging member 10 may optionallyundergo more than one color change. For example, image-forming layer 14may go from colorless to yellow to red as a function of the heatapplied. Image-forming layer 16 could initially be colored, then becomecolorless and then go to a different color. Those skilled in the artwill recognize that such color changes can be obtained by exploiting theimaging mechanism described in U.S. Pat. No. 3,895,173.

Any known printing modality may be used to provide a third image-forminglayer or additional image-forming layers beyond the two illustrated inFIG. 8. For example, the third image-forming layer may be imaged by inkjet printing, thermal transfer, electrophotography, etc. In particular,imaging member 10 may include a third image-forming layer which, aftercolor is formed in the layer, can then be fixed by exposure to light asis known in the art. In this embodiment, the third image-forming layershould be positioned close to the surface of imaging member 10 andprinted at a lower temperature than image-forming layer 14, prior to theprinting of image-forming layer 14. Fixation of this third layer shouldalso occur prior to printing of image-forming layer 14.

Substrate 12 may be of any suitable material for use in thermal imagingmembers, such as polymeric materials, and may be transparent orreflective.

Any combination of materials that may be thermally induced to changecolor may be used. The materials may react chemically under theinfluence of heat, either as a result of being brought together by aphysical mechanism, such as melting or diffusion, or through thermalacceleration of a reaction rate. The reaction may be chemicallyreversible or irreversible.

For example, a colorless dye precursor may form color upon heat-inducedcontact with a reagent. This reagent may be a Bronsted acid, asdescribed in “Imaging Processes and Materials”, Neblette's EighthEdition, J. Sturge, V. Walworth, A. Shepp, Eds., Van Nostrand Reinhold,1989, pp. 274-275, or a Lewis acid, as described for example in U.S.Pat. No. 4,636,819. Suitable dye precursors for use with acidic reagentsare described, for example, in U.S. Pat. No. 2,417,897, South AfricanPatent 68-00170, South African Patent 68-00323 and Ger. Offen.2,259,409. Further examples of such dyes may be found in “Synthesis andProperties of Phthalide-type Color Formers”, by Ina Fletcher and RudolfZink, in “Chemistry and Applications of Leuco Dyes”, Muthyala Ed.,Plenum Press, New York, 1997. Such dyes may comprise a triarylmethane,diphenylmethane, xanthene, thiazine or spiro compound, for example,Crystal Violet Lactone, N-halophenyl leuco Auramine, rhodamine Banilinolactam, 3-piperidino-6-methyl-7-anilinofluoran, benzoyl leucoMethylene blue, 3-methyl-spirodinaphthofuran, etc. The acidic materialmay be a phenol derivative or an aromatic carboxylic acid derivative,for example, p-tert-butylphenol, 2,2-bis (p-hydroxyphenyl)propane,1,1-bis(p-hydroxyphenyl) pentane, p-hydroxybenzoic acid,3,5-di-tert-butylsalicylic acid, etc. Such thermal imaging materials andvarious combinations thereof are now well known, and various methods ofpreparing heat-sensitive recording elements employing these materialsalso are well known and have been described, for example, in U.S. Pat.Nos. 3,539,375, 4,401,717 and 4,415,633.

The reagent used to form a colored dye from a colorless precursor mayalso be an electrophile, as described, for example, in U.S. Pat. No.4,745,046, a base, as described, for example, in U.S. Pat. No.4,020,232, an oxidizing agent, as described, for example, in U.S. Pat.Nos. 3,390,994 and 3,647,467, a reducing agent, as described, forexample, in U.S. Pat. No. 4,042,392, a chelatable agent, as described,for example, in U.S. Pat. No. 3,293,055 for spiropyran dyes, or a metalion, as described, for example, in U.S. Pat. No. 5,196,297 in whichthiolactone dyes form a complex with a silver salt to produce a coloredspecies.

The reverse reaction, in which a colored material is rendered colorlessby the action of a reagent, may also be used. Thus, for example, aprotonated indicator dye may be rendered colorless by the action of abase, or a preformed dye may be irreversibly decolorized by the actionof a base, as described, for example, in U.S. Pat. Nos. 4,290,951 and4,290,955, or an electrophilic dye may be bleached by the action of anucleophile, as described in U.S. Pat. No. 5,258,274.

Reactions such as those described above may also be used to convert amolecule from one colored form to another form having a different color.

The reagents used in schemes such as those described above may besequestered from the dye precursor and brought into contact with the dyeprecursor by the action of heat, or alternatively a chemical precursorto the reagents themselves may be used. The precursor to the reagent maybe in intimate contact with the dye precursor. The action of heat may beused to release the reagent from the reagent precursor. Thus, forexample, U.S. Pat. No. 5,401,619 describes the thermal release of aBronsted acid from a precursor molecule. Other examples ofthermally-releasable reagents may be found in “Chemical Triggering”, G.J. Sabongi, Plenum Press, New York (1987).

Two materials that couple together to form a new colored molecule may beemployed. Such materials include diazonium salts with appropriatecouplers, as described, for example, in “Imaging Processes andMaterials” pp. 268-270 and U.S. Pat. No. 6,197,725, or oxidizedphenylenediamine compounds with appropriate couplers, as described, forexample, in U.S. Pat. Nos. 2,967,784, 2,995,465, 2,995,466, 3,076,721,and 3,129,101.

Yet another chemical color change method involves a unimolecularreaction, which may form color from a colorless precursor, cause achange in the color of a colored material, or bleach a colored material.The rate of such a reaction may be accelerated by heat. For example,U.S. Pat. No. 3,488,705 discloses thermally unstable organic acid saltsof triarylmethane dyes that are decomposed and bleached upon heating.U.S. Pat. No. 3,745,009 reissued as U.S. Pat. No. Re. 29,168 and U.S.Pat. No. 3,832,212 disclose heat-sensitive compounds for thermographycontaining a heterocyclic nitrogen atom substituted with an —OR group,for example, a carbonate group, that decolorizes by undergoing homolyticor heterolytic cleavage of the nitrogen-oxygen bond upon heating toproduce an RO+ ion or RO′ radical and a dye base or dye radical whichmay in part fragment further. U.S. Pat. No. 4,380,629 disclosesstyryl-like compounds which undergo coloration or bleaching, reversiblyor irreversibly via ring-opening and ring-closing in response toactivating energies. U.S. Pat. No. 4,720,449 describes an intramolecularacylation reaction which converts a colorless molecule to a coloredform. U.S. Pat. No. 4,243,052 describes a pyrolysis of a mixed carbonateof a quinophthalone precursor which may be used to form a dye. U.S. Pat.No. 4,602,263 describes a thermally-removable protecting group which maybe used to reveal a dye or to change the color of a dye. U.S. Pat. No.5,350,870 describes an intramolecular acylation reaction which may beused to induce a color change. A further example of a unimolecularcolor-forming reaction is described in “New Thermo-Response Dyes:Coloration by the Claisen Rearrangement and Intramolecular Acid-BaseReaction Masahiko Inouye, Kikuo Tsuchiya, and Teijiro Kitao, Angew.Chem. Int. Ed. Engl. 31, pp. 204-5 (1992).

It is not necessary that the colored material formed be a dye. Thecolored species may also be, for example, a species such as a metal or apolymer U.S. Pat. No. 3,107,174 describes the thermal formation ofmetallic silver (which appears black) through reduction of a colorlesssilver behenate salt by a suitable reducing agent. U.S. Pat. No.4,242,440 describes a thermally-activated system in which apolyacetylene is used as the chromophore.

Physical mechanisms may also be used. Phase changes leading to changesin physical appearance are well known. The phase change may for examplelead to a change in scattering of light. Thermally-activated diffusionof dye from a restricted area, thereby changing its covering power andapparent density, has also been described in “A New ThermographicProcess”, by Shoichiro Hoshino, Akira Kato, and Yuzo Ando, Symposium onUnconventional Photographic System, Washington D.C. Oct. 29, 1964.

Image-forming layers 14 and 16 may comprise any of the image-formingmaterials described above, or any other thermally-activated colorants,and are typically from about 0.5 to about 4.0 μm in thickness,preferably about 2 μm. In the case where image-forming layers 14 and 16comprise more than one layer, each of the constituent layers aretypically from about 0.1 to about 3.0 μm in thickness. Image-forminglayers 14 and 16 may comprise dispersions of solid materials,encapsulated liquid, amorphous or solid materials or solutions of activematerials in polymeric binders, or any combinations of the above.

Interlayer 18 is typically from about 5 to about 30 μm in thickness,preferably about 14-25 μm. Interlayer 18 may comprise any suitablematerial including inert materials or materials which undergo a phasechange upon heating such as where the layer includes a thermal solvent.Typical suitable materials include polymeric materials such as poly(vinyl alcohol). Interlayer 18 may comprise one or more suitablematerials and can be made up of one or more layers. Interlayer 18 can becoated from aqueous or solvent solution or applied as a film laminatedto the image-forming layers. Interlayer 18 can be opaque or transparent.Where the interlayer is opaque, substrate 12 is preferably transparentso either outer surface of imaging member 10 can be printed with athermal printhead from one side. In a particularly preferred embodiment,substrate 12 is transparent and interlayer 18 is white. The effect oftwo-sided printing of a single sheet using only a single thermalprinthead, printing on only one side of said sheet, is thereby obtained.

The thermal imaging members of the invention may also include thermalbackcoat layers and protective topcoat layers arranged over the outersurface of the image-forming layers. In a preferred embodiment of theimaging member shown in FIG. 8, there are included a barrier coating anda protective topcoat layer over layer 14. The barrier layer may comprisewater and gas inhibiting materials. Taken together, the barrier andtopcoat layers may provide protection from UV radiation.

In an alternative embodiment of the imaging member shown in FIG. 8,image-forming layer 16 is coated on a thin substrate 12 such as, forexample, poly(ethylene terephthalate) having a thickness of about 4.5μm. Interlayer 18 and image-forming layer 14 are then deposited.Substrate 12 may be opaque or transparent and can be coated, laminatedor extruded onto layer 16. In this embodiment of the invention,image-forming layers 14 and 16 can be addressed by a thermal printheador printheads through the thin substrate 12.

Referring now to FIG. 9 there is seen a three color thermal imagingmember according to the invention that utilizes thermal delays to definethe printing regions for the colors to be formed. The three colorimaging member 20 includes substrate 22, cyan, magenta and yellowimage-forming layers, 24, 26 and 28, respectively, and spacerinterlayers 30 and 32. Preferably, interlayer 30 is thinner thaninterlayer 32 so long as the materials comprising both layers have thesame heat capacity and thermal conductivity. The activation temperatureof layer 24 is higher than that of layer 26 which in turn is higher thanthat of layer 28.

According to a preferred embodiment of the invention a thermal imagingmember in which a plurality of image-forming layers are carried by thesame surface of a substrate, as is illustrated in FIG. 9 where threeimage-forming layers are carried by the same surface of substrate 22,two of the image-forming layers can be imaged by one or more thermalprintheads from one surface of the member and at least a thirdimage-forming layer imaged by a separate thermal printhead from theopposite side of the substrate. In the embodiment illustrated in FIG. 9,image-forming layers 24 and 26 are imaged by one or two thermalprintheads in contact with the outer surface of color-forming layer 24and color-forming layer 28 is imaged by a thermal printhead in contactwith the outer surface of substrate 22. In this embodiment of theinvention, substrate 22 is relatively thin and is typically less thanabout 20 μm and preferably about 5 μm thick.

In this instance, since the substrate 22 is relatively thin, it ispreferred to laminate the imaged member to another base such as labelcard stock material. Such laminate structures can also provideadditional features such as where the image-forming layers are designedto separate when the laminated structure is taken apart, thus providingsecurity features. Also, ultraviolet and infrared security features canbe incorporated into the image-forming layers.

By laminating the imaged thermal imaging member to another base, anumber of product applications are provided. The base stock can beanything that will support an adhesive bonding agent. Thus, imaging canbe carried out on various materials such as transparent or reflectivesticker materials which can be laminated onto transparent or reflectivecarrier materials to provide transparencies or reflective products.

FIG. 10 illustrates a multicolor thermal imaging member according to theinvention wherein two image-forming layers are arranged on one side of asubstrate and one image-forming layer is arranged on the other side ofthe substrate. Referring now to FIG. 10 there is seen imaging member 40which includes a substrate 42, a first image-forming layer 44,interlayer 46, a second image-forming layer 48, a third image-forminglayer 50, an optional white or reflective layer 52, a backcoat layer 53and a topcoat layer 54. In this preferred embodiment substrate 42 istransparent. The image-forming layers and the interlayer may compriseany of the materials described above for such layers. Optional layer 52may be any suitable reflective material or may comprise particles of awhite pigment such as titanium dioxide. Protective topcoat and backcoatlayers 53 and 54 may comprise any suitable materials providing thefunctions of lubrication, heat resistance, UV, water and oxygen barrierproperties, etc. Such materials may comprise polymeric binders in whichappropriate small molecules are dissolved or dispersed, as will befamiliar to those skilled in the art. The activation temperature ofimage-forming layer 48 is lower than that of image-forming layer 44 andthe activation temperature of image-forming layer 50 can be the same asthat of image-forming layer 48 or higher or lower and may be as low aspossible consistent with the requirement of room temperature andshipping stability.

In a preferred embodiment, one thermal printhead can be utilized toaddress independently from one surface of the imaging member twoimage-forming layers carried by one surface of a substrate and anotherthermal printhead utilized to address independently from the opposingsurface of the imaging member one or more image-forming layers carriedby the opposing surface of the substrate. This preferred embodiment ofthe invention will be described further in detail with respect to theimaging member shown in FIG. 10 although it will be understood that theembodiment may be practiced with other suitable imaging members. Thethermal printheads which are brought into contact with opposing surfacesof the imaging member can be arranged directly opposite to each other.Alternatively, and preferably, the respective printheads are offset fromeach other as is illustrated in FIG. 11. Further, two separate thermalprint engines such as an Alps MBL 25, available from Alps Electric Co.Ltd., Tokyo, Japan can be used. However, it is preferred to utilize athermal printing apparatus where some of the components such as thedrive motor and power source are shared by the two print stations.

Referring now to FIG. 11 there is seen a roll of a thermal imagingmember 55, for example, the imaging member illustrated in FIG. 10. Theimaging member is passed between a first thermal printhead 56 andbacking roller 57 and subsequently between a second thermal printhead 58and backing roller 59. First thermal printhead 56 addresses at leastpartially independently the first and second image-forming layers 44 and48, which may be cyan and magenta image-forming layers respectively andsecond thermal printhead 58 addresses third image-forming layer 50 whichmay be a yellow image-forming layer.

As discussed previously, in the advantageous multicolor thermal imagingmethod of the invention, two or more different image-forming layers of athermal imaging member are addressed at least partially independentlyfrom the same surface of the imaging member by a single thermalprinthead or multiple thermal printheads. In a particularly preferredembodiment of the invention, two or more different image-forming layersof a thermal imaging member are addressed at least partiallyindependently by a single thermal printhead in a single pass. Themethods for doing so can be carried out by the manipulation of controlsignals applied to a conventional thermal printhead, the heatingelements of which are in contact with a surface of the imaging member. Aconventional thermal printhead is composed of a linear array of heatingelements, each having a corresponding electronic switch capable ofconnecting it between a common voltage bus and ground. The voltage ofthe common bus and the time that the electrical switch is closed willtogether affect the temperature and time of the thermal exposure.

In order to describe the methods for controlling temperature in thepractice of the invention, the operation of the thermal printhead willnow be described in more detail. In normal use of the printhead, a fixedvoltage is applied to the printhead and the modulation of density on theimage formed is achieved by controlling the length of time that power isapplied to the heating elements. The control system may be discrete,that is, the time interval used to print each pixel on the imagingmember is divided into a number of discrete subintervals and the heatingelement may be either active or inactive during each of thesubintervals. Moreover, the duty cycle of the heating within eachsubinterval may be controlled. For example, if a heating element isactive during one of the subintervals and the duty cycle for thatsubinterval is 50%, then power will be applied to the heating elementduring 50% of that particular subinterval. This process is illustratedin FIG. 12.

FIG. 12 illustrates a printhead application in which each pixel-printinginterval is divided into seven equal subintervals. For the caseillustrated, the pixel is active for the first four subintervals andthen inactive for three subintervals. In addition, the voltage pulsesthat are applied have a 50% duty cycle, so that within each activesubinterval, the voltage is on for half of the subinterval and off forthe other half. Insofar as the temperature of the heating element isresponsive to the power applied, it is easily appreciated by thoseskilled in the art that this temperature may be affected by the commonbus voltage and by the duty cycle of the pulses. In fact, if theindividual subintervals are much shorter than the thermal time constantfor heating and cooling of the medium, then the effect of changing thevoltage of the common bus may be mimicked by the effect of changing theduty cycle of the pulses.

This offers at least two possibilities for controlling the average powerapplied to the printhead. The first is that the temperature of aprinthead heating element may be controlled by manipulating the voltageon the common bus, while the duty cycle remains fixed at somepredetermined values for each subinterval. In this instance, thetemperature is controlled primarily by the choice of bus voltage, andthe time is controlled by the selection of the number of subintervalsfor which the heater is activated.

The second possibility is the control of the heater temperature bymanipulation of the duty cycles of the subintervals while the busvoltage remains fixed. Best use of this method of temperature controlrequires that the subintervals be short compared to the thermaltime-constant of the imaging member, so that the temperature in theimage-forming layer responds to the average power applied during thesubinterval rather than tracking the rapid voltage transitions. For atypical printhead in this application, the subinterval time may be tenor more times shorter than the thermal response time of the imagingmember so this condition is well satisfied.

The choice between these two methods of control, or of a combination ofthe two, is a matter of practical design. For example, in amultiple-pass system in which each color layer is printed in a separatepass of the imaging member beneath the printhead, it is not difficult tochange the voltage applied to the printhead common bus on each pass. Theapplied voltages can then be easily adjusted for best results. On theother hand, for a single-pass system in which two or more color layersare written in quick succession at each pixel, it is generally moreconvenient and economical to operate the head at a fixed voltage. Inthis case the temperature changes are preferably effected by apredetermined sequence of duty cycles of the subintervals.

The two techniques are illustrated in FIGS. 13 and 14 which are based ona two image-forming layer system in which one image-forming layer isactivated by a high temperature applied for short times, and the otherimage-forming layer is activated by a lower temperature applied forlonger times.

FIG. 13 illustrates schematically a method of alternately writing on thetwo image-forming layers by changing the bus voltage and the time overwhich the heater is activated. Initially the writing is athigh-temperature for a short time, and is accomplished by a short seriesof high voltage pulses. Subsequently, writing is done at a lowtemperature for a long time by using a longer sequence of lower-voltagepulses. The sequence then repeats to alternate back and forth betweencolor-forming layers.

FIG. 14 illustrates schematically another method of alternately writingon two image-forming layers. In this case the pulse duty cycle is variedrather than the pulse voltages. The high-temperature, short-time heatingis performed with a short sequence of pulses having a large duty cycle.The low-temperature, long-time heating is performed with a longersequence of pulses having a low duty cycle.

The method illustrated in FIG. 14 for forming an image in an imagingmember of the invention with two image-forming layers will now bedescribed in more detail. The time interval for forming a single pixelof an image in the region of the thermal imaging member that is inthermal contact with a heating element of the printhead is divided intoa plurality of temporal subintervals (hereinafter referred to asmini-subintervals), as described above. The mini-subintervals may beequal or different in duration to each other. In a preferred embodiment,the mini-subintervals are of equal duration. The time interval forforming a single pixel is also divided into a first and a second timeinterval, the first time interval being shorter than the second timeinterval. The first time interval is used to form an image in a firstcolor-forming layer of the thermal imaging member (which may be ahigher-temperature color-forming layer), and the second time interval isused to form an image in a second color-forming layer of the thermalimaging member (which may be a lower-temperature color-forming layer).The first time interval and the second time interval will, between them,contain most or all of the mini-subintervals described above. In thecase when the mini-subintervals are of equal duration, the first timeinterval will contain fewer mini-subintervals than the second timeinterval. It is preferred that the second time interval be at leasttwice as long as the first time interval. It is not necessary that thefirst time interval precede the second time interval. It is possiblethat, in combination, the first time interval and the second timeinterval do not occupy the entire time interval for printing a singlepixel. However, it is preferred that, in combination, the first timeinterval and the second time interval occupy most of the time intervalfor printing a single pixel.

A heating element of the printhead is activated by applying a singlepulse of electrical current during a mini-subinterval. The proportion ofthe duration of the mini-subinterval (i.e., the duty cycle) during whichthis pulse of electrical current is applied may take any value betweenabout 1% and 100%. In a preferred embodiment, the duty cycle is a fixedvalue, p1, during the first time interval, and a second fixed value, p2,during the second time interval, and p1>p2. In a preferred embodiment,p1 approaches 100%. It is preferred that p1 be greater than or equal totwice the length of p2.

Within the first time interval and the second time interval, differentdegrees of image formation within the image-forming layers (i.e.,different gray levels of the image) may be achieved by selecting aparticular group of mini-subintervals, from among the total number ofmini-subintervals available, during which a pulse of electrical currentwill be applied. The different degrees of image formation may beachieved either by changing the size of dots printed in theimage-forming layer(s), or by changing the optical density of dotsprinted in the image-forming layer(s), or by a combination of variationsin dot size and optical density.

Although the method has been described above with reference to a singlepixel, printed by a single heating element of the printhead, it will beapparent to one of skill in the art that a printhead may contain alinear array of many such heating elements, and that the thermal imagingmember may be translated beneath this linear array, in a directionorthogonal to said linear array, such that an image of a line of pixelsmay be formed in the thermal imaging member during the time interval forforming an image of a single pixel by a single heating element. Further,it will be clear to one of skill in the art that images may be formed ineither or both of the image-forming layers of the thermal imaging memberduring the time interval for forming an image of a single pixel by asingle heating element, the image in the first image-forming layer beingformed by the energy applied during the first time interval specifiedabove, and the image formed in the second image-forming layer beingformed by the energy applied during the second time interval specifiedabove. Thus, both images may be formed when the thermal imaging memberis translated once beneath the printhead, i.e., in a single pass of theprinthead. In practice, the energy applied during the first time periodwill heat the second image-forming layer, and the energy applied duringthe second time period will heat the first image-forming layer. Those ofskill in the art will appreciate that suitable adjustment of the energysupplied during both time periods will be required in order tocompensate for these effects, as well as to compensate for othereffects, such as thermal history and unintended heating by adjacentheating elements.

In actual practice, the number of pulses can be quite different thanthat shown in FIGS. 13 and 14. In a typical printing system, thepixel-printing interval may be in the range of 1-100 milliseconds andthe mini-subinterval length may be in the range of 1-100 microseconds.There are therefore typically hundreds of mini-subintervals within thepixel-printing interval.

The duty cycle within a mini-subinterval can generally be changed frompulse to pulse and, in another preferred embodiment, this technique maybe used to tailor the average power applied to the heating elements toachieve good printing results.

Of course, it will be apparent to those skilled in the art that where itis desired to address independently more than two image-forming layersof the imaging member in a single pass, the available number ofmini-subintervals and the range of duty cycles must be divided into acorrespondingly larger number of combinations, each capable of printingat least partially independently on one of the image-forming layers.

In a particularly preferred embodiment of the invention, three differentimage-forming layers carried by the same surface of the substrate of thethermal imaging member are addressed from the same surface of theimaging member by one thermal printhead in a single pass. Thisembodiment will be described in relation to FIG. 9. The substrate 22 maybe any of the materials previously described. Image-forming layer 28comprises a meltable leuco dye having a melting point of from about 90°C. to about 140° C. and a developer material having a melting point inthe same range, and optionally includes a thermal solvent having amelting point in the same range. In this embodiment layer 28 is about 1to 4 μm thick and is coated from an aqueous dispersion. Interlayer 32 isabout 5 to about 25 μm thick and comprises a water-soluble inertmaterial which may be any suitable water-soluble interlayer materialpreviously mentioned. The second image-forming layer, 26, comprises aleuco dye and a developer material, each having a melting point of fromabout 150° C. to about 280° C., and optionally includes a thermalsolvent having a melting point in the same range. The secondimage-forming layer has a thickness of from about 1 to about 4 μm and iscoated from a water dispersion. The second interlayer, 30, comprises awater-soluble inert material, which may be any of the water-solubleinterlayer materials previously mentioned, and has a thickness of fromabout 3 to about 10 μm. The third image-forming layer, 24, compriseseither: a) a meltable leuco dye having a melting point of at least 150°C., preferably 250° C., and a developer material having a melting pointof at least 250° C., preferably 300° C., optionally including a thermalsolvent; or b) a molecule which forms color unimolecularly at atemperature of at least 300° C. in about from 0.1 to about 2milliseconds (a suitable material is Leuco Dye III described in detailbelow herein). The third image-forming layer has a thickness of fromabout 1 to about 4 μm and is coated from a water dispersion. Thisparticularly preferred thermal imaging member further includes anovercoat layer such as is described in Example I below.

As described above, FIGS. 8-10 relate to a thermal imaging member forwhich thermal diffusion is the technique used for partitioning thetime-temperature domain. Another technique for partitioning thetime-temperature domains of a thermal imaging member in accordance withthe invention resides in the exploitation of phase transitions. Thephase transitions, for example, may be the result of a natural meltingor glass transitions of the dye itself, or may be achieved byincorporating thermal solvents into the dye layers. When a measurementis made of the time t required to reach a certain optical density of thedye when the dye layer is held at a fixed temperature T it is typicallyfound that the relationship between the temperature and the time isexpressed by an Arrhenius curve:

log(t)˜(−A+B/T)

where A and B are constants that may be determined experimentally. Whenmeasurements are taken in the temperature range of a melting transition,it is often found that the slope, B, far exceeds that normally found inregions removed from phase transitions. As a result, the Arrhenius curvefor a normal dye layer (i.e., one in which no phase change is associatedwith imaging, as will be the case for diffusion-controlled reactions,for example) and for a melting dye layer may cross at a steep angle, asshown in FIG. 15 for a cyan dye, namely3-(1-n-butyl-2-methylindol-3-yl)-3-(4-dimethylamine-2-methylphenyl)phthalide,available from Hilton-Davis Company, in conjunction with a Lewis Aciddeveloper, the zinc salt of 3,5-di-t-butylsalicylic acid and a naturallymelting magenta dye, namely Solvent Red 40, available from YamamotoChemical Company in conjunction with an acid developer,bis(3-allyl-4-hydroxyphenyl) sulfone, available from Nippon KayakuCompany, Ltd. The two curves show the time required to reach a densityof 0.1 for each dye. Such a relationship may itself be used as the basisfor a multicolor thermal printing system according to one embodiment ofthe present invention, insofar as FIG. 15 shows that below the crossingtemperature the cyan dye turns on more quickly than the magenta dye andabove the crossing temperature the magenta dye turns on more quicklythan the cyan dye. For the two dyes shown, it is seen that it would takemore than one second per line to print cyan without magentacontamination. To overcome this limitation, the dyes or theirenvironment may be modified to move the crossing point to a shorter timeregion. However, the system may be made even more desirable from a timeconsideration by “burying” the magenta dye layer as described above inFIG. 8.

Yet another technique for partitioning the time-temperature domains of athermal imaging member in accordance with the invention is illustratedin FIG. 16. This technique employs a multicolor thermal imaging member60 according to the invention which includes a layer of a magentaimage-forming material 62, in this illustrative instance a leuco dye,associated with a layer 64 of an acid developer material having amelting point, T₇ and a layer of a cyan image forming material 66associated with a layer 68 of an acid developer material having amelting point, T₈. The imaging member 60 also includes first and secondtiming layers, 70 and 72, respectively, and a layer 74 of a fixingmaterial having a melting point, T₉. Imaging member 60 may also includea substrate (not shown) which may be positioned adjacent layer 64 orlayer 68.

There are known leuco dyes that form color irreversibly upon contactwith suitable developers. With this type of dye, layer 74 of fixingmaterial functions to terminate, but not reverse, color formation ineither of the two image-forming layers, 62 and 66, respectively. Thefixing material, however, must pass through the timing layers, 70 and72, respectively, by diffusion or dissolution to terminate colorformation within the image-forming layers. As shown, one of the timinglayers, in this illustrative instance timing layer 70, is thinner thanthe other timing layer 72 and therefore the fixing material arrives atcyan image-forming layer 66 later than when it arrives at magentaimage-forming layer 62. Thus, a timing difference is introduced betweenthe formation of the two colors in accordance with the invention.

The developer layers 64 and 68 must melt before the developer materialscan combine with the leuco dyes. By selecting the materials in thedeveloper layer such that they melt at different temperatures, atemperature difference is introduced between the formation of the twocolors in accordance with the invention. In this illustrative embodimentT₇ is lower than T₈, e.g., T₇=120° C. and T₈=140° C. In this embodimentof the invention various possibilities are provided. Where the imagingmember is heated to a temperature less than 120° C., then neither of thedeveloper layers, 64 and 68, will melt and no color will be formed.Further, provided that the thermal energy applied to the imaging memberis sufficient to melt the fixing material, the melting point of thefixing layer, T₉, being less than the melting points, T₇ and T₈,respectively, of the developer layers, (e.g., T₉=100° C.) the fixingmaterial will diffuse through the timing layers 70 and 72 and eventuallyfix both image-forming layers so that subsequent temperatureapplications will not cause any color to form.

When the imaging member 60 is heated to a temperature between T₇ and T₈then developer material in layer 64 will melt and begin to mix with themagenta leuco dye precursor to form color. The amount of color formationis dependent primarily upon the amount of time the temperature of thedeveloper layer 64 remains above T₇. Following this thermal exposure thetemperature of the imaging member is lowered below T₇ and held at thattemperature until the fixing material arrives and prevents any furthercolor formation. When the temperature of the imaging member is heldbelow T₇ for a longer period of time the fixing material will alsoarrive at the cyan image-forming layer 66 and prevent any futureformation of color by this layer. In this manner a selectable amount ofmagenta color can be formed without forming any cyan color.

In a similar manner a selectable amount of cyan can be formed inaccordance with the invention without forming any magenta. Initially,the imaging member is heated to a temperature above T₉ but below T₇ inorder to to allow the fixing material to arrive at magenta image-forminglayer 62 and inactivate it, thereby preventing it from subsequentlyforming any color. Subsequently, the temperature is raised above T₈ tocause the developer material in layer 68 to combine with the cyan leucodye precursor and begin the formation of cyan color. The amount of cyancolor formation is primarily dependent upon the amount of time thetemperature of the imaging member is maintained above T₈. It will beappreciated that this procedure will also cause the developer materialin layer 64 to melt but no formation of magenta color results since themagenta dye precursor was previously fixed. Subsequently, thetemperature of the imaging member 60 is lowered below T₇ and held atthat level until the fixing material arrives at layer 66 to prevent theformation of any further cyan.

In order to print both magenta and cyan, the sequence of heat pulsesapplied to the imaging member 60 is such as to carry out a combinationof the steps described above to create cyan and magenta, respectively.Initially, the imaging member 60 is heated to a temperature above T₇ toproduce a selectable density of magenta. The temperature is then loweredbelow T₇ for a period of time sufficient to fix the magenta precursorlayer 62 followed by raising the temperature above T₈ to produce aselectable density of cyan color and then once again lowering thetemperature below T₇ to fix the cyan precursor layer 66.

As previously described, a wide variety of different irreversiblechemical reactions may be used to achieve a color change in a layer. Thefixer material used in any particular instance will depend upon thechoice of mechanism exploited to achieve the color change. For example,the mechanism may involve the coupling of two colorless materials toform a colored dye. In this case, the fixing reagent would react witheither of the two dye precursor molecules to form a colorless productthereby interfering with any further formation of dye.

A negative working version of a two-color imaging member according tothe invention may also be devised according to the same principles, asillustrated in FIG. 17. In this implementation the dye layers areinitially colored, and they remain so unless an adjacent layer ofdecolorizing reagent thermally activated before the arrival of thefixing reagent through a timing layer. Referring now to FIG. 17 there isseen a negative working thermal imaging member 80 according to theinvention which includes a first image-forming layer 82, e.g., a magentadye layer, a second image-forming layer 84, e.g., a cyan dye layer,first and second timing layers 86 and 88, respectively, a fixing layer90 and first and second decolorizer layers 92 and 94, respectively.Imaging member 80 may also include a substrate (not shown) which may bepositioned adjacent layer 92 or layer 94.

For example, the magenta and cyan dyes may be irreversibly decolorizedby exposure to a base as described in U.S. Pat. Nos. 4,290,951 and4,290,955. Where the reagent layer 90 contains an acidic material andthe acid is chosen so as to neutralize the basic material in thedecolorizing layers 92 and 94, it will be appreciated that where theacid arrives in the dye-containing layers before the base, the base willnot be able to decolorize the magenta or cyan dye whereas when the basearrives before the acid, irreversible decolorization will have occurred.As discussed above in relation to the embodiment shown in FIG. 8, thethird color may be obtained by any other printing modality includingthermally printing the third color from the back of the imaging memberas described in relation to FIGS. 9 and 10.

FIG. 18 illustrates a three-color thermal imaging member according tothe invention. Referring now to FIG. 18 there is seen imaging member 100which includes the layers shown for the imaging member 60 which isillustrated in FIG. 16 and these layers are designated by the samereference numerals. Imaging member 100 also includes a buffer layer 102,yellow dye precursor layer 104 and a third acid developer layer 106 inwhich the developer material has a melting point T₁₀ which is higherthan T₇ and T₈. After forming the desired color densities in cyan andmagenta as described above in relation to FIG. 16, the temperature ofthe imaging member can be raised above T₁₀ to form a selectable densityof yellow dye. It should be noted that where T₁₀ is a temperature higherthan the imaging member 100 is likely to encounter during its usefullife, it is not necessary to inactivate the yellow dye precursorsubsequent to writing the yellow image. Imaging member 100 may alsoinclude a substrate (not shown) which may be positioned adjacent layer64 or layer 106.

In choosing the layer dimensions for the imaging members illustrated inFIGS. 16 and 18 it is advantageous to have the timing layer 70 be asthin as possible but not substantially thinner than dye layer 62. Timinglayer 72 typically will be about two to three times the thickness oftiming layer 70.

It will be appreciated that the practice of the invention according tothe methods just described relies upon the diffusion or dissolution ofchemical species, rather than the diffusion of heat. Whereas the thermaldiffusion constant is normally relatively insensitive to temperature,the diffusion constants for chemical diffusion are typicallyexponentially dependent on the inverse of the temperature, and thereforemore sensitive to changes in the ambient temperature. Moreover, whendissolution is chosen as the time-determining mechanism, numericalsimulations show that the timing is typically quite critical because thecolorization process occurs relatively quickly once the timing layer hasbeen breached.

Any chemical reaction in which color is formed irreversibly is, inprinciple, amenable to the fixing mechanism described above. Materialsthat form color irreversibly include those in which two materials coupletogether to form a dye. The fixing mechanism is achieved by introducinga third reagent that couples preferentially with one of the twodye-forming materials to form a colorless product.

In addition to the methods recited above, chemical thresholds can alsobe used to partition the time-temperature domain in accordance with themulticolor thermal imaging system of the invention. As an example ofthis mechanism, consider a leuco dye reaction in which the dye isactivated when it is exposed to an acid. If, in addition to the dye, themedium contains a material significantly more basic than the dye, whichdoes not change color when protonated by the acid, addition of acid tothe mixture will not result in any visible color change until all of themore basic material has been protonated. The basic material provides fora threshold amount of acid which must be exceeded before any colorationis evident. The addition of acid may be achieved by various techniquessuch as by having a dispersion of acid developer crystals which melt anddiffuse at elevated temperatures or by having a separate acid developerlayer which diffuses or mixes with the dye layer when heated.

A certain time delay is involved in reaching the acid level required toactivate the dye. This time period may be adjusted considerably byadding base to the imaging member. In the presence of added base, asdescribed above, there is an interval of time required for theincreasing amount of acid to neutralize the base. Beyond this timeperiod, the imaging member will be colorized. It will be seen that thesame technique can be used in a reverse sequence. A dye that isactivated by base can have its timing increased by the addition of abackground level of acid.

In this particular embodiment, it is notable that the diffusion of theacid or base developer material into the dye-containing layer istypically accompanied by diffusion of dye in reverse into the developerlayer. When this occurs, color formation may begin almost immediatelysince the diffusing dye may find itself in an environment where thedeveloper material level far exceeds the threshold level necessary toactivate the dye. Accordingly, it is preferred to inhibit the dye fromdiffusing into the developer layer.

This may be accomplished, for example, by attaching long molecularchains to the dyes, by attaching the dyes to a polymer, or by attachingthe dye to an ionic anchor.

EXAMPLES

The thermal imaging system of the invention will now be describedfurther with respect to specific preferred embodiments by way ofexamples, it being understood that these are intended to be illustrativeonly and the invention is not limited to the materials, amounts,procedures and process parameters, etc. recited therein. All parts andpercentages are by weight unless otherwise specified.

The following materials were used in the examples described below:

Leuco Dye I, 3,3-bis(1-n-butyl-2-methyl-indol-3-yl)phthalide (Red 40,available from Yamamoto Chemical Industry Co., Ltd., Wakayama, Japan);

Leuco Dye II,7-(1-butyl-2-methyl-1H-indol-3-yl)-7-(4-diethylamino-2-methyl-phenyl)-7H-furo[3,4-b]pyridin-5-one(available from Hilton-Davis Co., Cincinnati, Ohio);

Leuco Dye III,1-(2,4-dichloro-phenylcarbamoyl)-3,3-dimethyl-2-oxo-1-phenoxy-butyl]-(4-diethylamino-phenyl)-carbamicacid isobutyl ester, prepared as described in U.S. Pat. No. 5,350,870;

Leuco Dye IV, Pergascript Yellow I-3R, available from Ciba SpecialtyChemicals Corporation, Tarrytown, N.Y.;

Acid Developer I, bis(3-allyl-4-hydroxyphenyl)sulfone, available fromNippon Kayaku Co., Ltd, Tokyo, Japan;

Acid Developer II, PHS-E, a grade of poly(hydroxy styrene), availablefrom TriQuest, LP, a subsidiary of ChemFirst Inc., Jackson, Miss.;

Acid Developer III, zinc salt of 3,5-di-t-butyl salicylic acid,available from Aldrich Chemical Co., Milwaukee, Wis.;

Acid Developer IV, zinc salt of 3-octyl-5-methyl salicylic acid,prepared as described in Example 7 below;

Airvol 205, a grade of poly(vinyl alcohol) available from Air Productsand Chemicals, Inc., Allentown, Pa.;

Airvol 350, a grade of poly(vinyl alcohol) available from Air Productsand Chemicals, Inc., Allentown, Pa.;

Airvol 540, a grade of poly(vinyl alcohol) available from Air Productsand Chemicals, Inc., Allentown, Pa.;

Genflo 305, a latex binder, available from Omnova Solutions, Fairlawn,Ohio;

Genflo 3056, a latex binder, available from Omnova Solutions, Fairlawn,Ohio;

Glascol C44, an aqueous polymer dispersion, available from CibaSpecialty Chemicals Corporation, Tarrytown, N.Y.;

Joncryl 138, a binder, available from S.C. Johnson, Racine, Wis.;

Irganox 1035, an antioxidant, available from Ciba Specialty ChemicalsCorporation, Tarrytown, N.Y.;

Aerosol-OT, a surfactant available from Dow Chemical, Midland, Mich.;

Dowfax 2A1, a surfactant available from Dow Chemical Corporation,Midland, Mich.;

Ludox HS40, a colloidal silica available from DuPont Corporation,Wilmington, Del.;

Nipa Proxel, a bactericide available from Nipa Inc., Wilmington, Del.;

Pluronic 25R2, a surfactant available from BASF, Ludwigshaven, Germany;

Tamol 731, a polymeric surfactant (sodium salt of polymeric carboxylicacid) available from Rohm and Haas Company, Philadelphia, Pa.;

Triton X-100, a surfactant available from Dow Chemical Corporation,Midland, Mich.;

Zonyl FSN, a surfactant, available from DuPont Corporation, Wilmington,Del.;

Zonyl FSA, a surfactant, available from DuPont Corporation, Wilmington,Del.;

Hymicron ZK-349, a grade of zinc stearate available from CytechProducts, Inc., Elizabethtown, Ky.;

Klebosol 30V-25, a silica dispersion available from ClariantCorporation, Muttenz, Switzerland;

Titanium dioxide, a pigment available from DuPont Corporation,Wilmington, Del.;

Glyoxal, available from Aldrich Chemical Co., Milwaukee, Wis.;

Melinex 534, a white poly(ethylene terephthalate) film base ofapproximately 96 microns' thickness, available from DuPont Corporation,Wilmington, Del.);

Cronar 412, a clear poly(ethylene terephthalate) film base ofapproximately 102 microns' thickness, available from DuPont Corporation,Wilmington, Del.

Example I

A two color imaging member such as is illustrated in FIG. 8 and furtherincluding an overcoat layer deposited on the cyan color-forming layerwas prepared as follows:

The magenta image-forming layer was prepared as follows:

A leuco magenta dye, Leuco Dye I, was dispersed in an aqueous mixturecomprising Airvol 205 (4.5% of total solids) and surfactants Pluronic25R2 (1.5% of total solids) and Aerosol-OT (5.0% of total solids) indeionized water, using an attriter equipped with glass beads, stirredfor 18 hours at 2° C. The average particle size of the resultingdispersion was about 0.28 microns and the total solid content was19.12%.

Acid Developer I was dispersed in an aqueous mixture comprising Airvol205 (7.0% of total solids), Pluronic 25R2 (1.5% of total solids), anddeionized water, using an attriter equipped with glass beads and stirredfor 18 hours at 2° C. The average particle size of the resultingdispersion was about 0.42 microns, and the total solid content was29.27%.

The above dispersions were used to make the magenta coating fluid inproportions stated below. The coating composition thus prepared wascoated onto Melinex 534 using a Meyer rod, and dried. The intendedcoating thickness was 2.9 microns.

Ingredient % solids in dried film Leuco Dye I 10.74% Acid Developer I42.00% Genflo 3056 47.05% Zonyl FSN 0.21%

A thermally insulating interlayer was deposited onto the magenta imaginglayer as follows:

A coating fluid for the interlayer was prepared in proportions statedbelow. The image interlayer coating composition thus prepared was coatedon the magenta imaging layer using a Meyer rod for an intended thicknessof 13.4 microns, and was dried in air.

Ingredient % solids in dried film Glascol C44 99.50% Zonyl FSA 0.50%

Cyan image-forming layers C1-C3 were deposited on the thermallyinsulating layer as follows:

C1 Cyan developer layer.

Acid Developer III was dispersed in an aqueous mixture comprising ofAirvol 205 (6.0% of total solids), Aerosol-OT (4.5% of total solids) andTriton X-100 (0.5% of total solids) in deionized water, using anattriter equipped with glass beads, by stirring for 18 hours at roomtemperature. The average particle size of the resulting dispersion wasabout 0.24 microns, and the total solid content was 25.22%.

The above dispersion was used to make the cyan developer coating fluidin proportions stated below. The cyan developer coating composition thusprepared was coated on top of the imaging interlayer using a Meyer rodfor an intended thickness of 1.9 microns, and was dried in air.

Ingredient % solids in dried film Joncryl 138 9.50% Acid Developer III89.50% Zonyl FSN 1.00%

C2 Cyan interlayer.

A cyan interlayer coating fluid was prepared in proportions statedbelow. The cyan interlayer coating composition thus prepared was coatedon top of the cyan developer layer using a Meyer rod for an intendedthickness of 2.0 microns, and was dried in air.

Ingredient % solids in dried film Airvol 205 99.00% Zonyl FSN 1.00%

C3 Cyan dye layer.

The leuco cyan dye, Leuco Dye II, was dispersed in an aqueous mixturecomprising Airvol 350 (7.0% of total solids), Airvol 205 (3.0% of totalsolids), Aerosol-OT (1.0% of total solids) and Triton X-100 (0.2% oftotal solids) in deionized water, using an attriter equipped with glassbeads, stirred for 18 hours at room temperature. The average particlesize of the resulting dispersion was about 0.58 microns, and the totalsolid content was 26.17%.

The above dispersion was used to make the cyan coating fluid inproportions stated below. The cyan coating composition thus prepared wascoated on the cyan interlayer using a Meyer rod for an intendedthickness of 0.6 microns, and was dried in air.

Ingredient % solids in dried film Leuco Dye II 59.5% Joncryl 138 39.5%Zonyl FSN 1.0%

A protective overcoat was deposited on the cyan color-forming layers asfollows:

A slip overcoat was coated on the cyan dye layer. The overcoat wasprepared in proportions stated below. The overcoat coating compositionthus prepared was coated on the cyan dye layer using a Meyer rod for anintended thickness of 1.0 micron, and was dried in air.

Ingredient % solids in dried film Glyoxal 9.59% Hymicron ZK-349 31.42%Klebosol 30V-25 23.53% Zonyl FSA 3.89% Airvol 540 31.57%

The resulting six-layer imaging member was printed using a laboratorytest-bed printer equipped with a thermal head, model KST-87-12 MPC8(Kyocera Corporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan).

The following printing parameters were used:

Printhead width: 3.41 inchPixels per inch: 300Resistor size: 69.7×80 microns

Resistance: 3536 Ohm

Line Speed: 8 milliseconds per linePrint speed: 0.42 inches per secondPressure: 1.5-2 lb/linear inchDot pattern: Rectangular grid.

The cyan layer was printed with a high power/short time condition. Inorder to obtain gradations of color, the pulse width was increased fromzero to a maximum of 1.3 milliseconds (about 16.3% of the total linetime) in twenty equal steps, while the voltage supplied to the printhead was maintained at 27.0V.

A lower power/longer time condition was used to print the magenta layer.The pulse width was increased from zero to the full 8 millisecond linetime in twenty equal steps, while the voltage supplied to the print headwas maintained at 14.5V.

Following printing, the reflection density in each of the printed areaswas measured using a spectrophotometer from GretagMacbeth A G,Regensdorf, Switzerland. The results are shown in Tables I and II. TableI shows the printing of the cyan layer as a function of energy suppliedby the thermal head. The magenta densities obtained are shown as well.Also included in Table I is the ratio between the cyan and the magentadensity (C/M). Similarly, Table II shows the printing of the magentalayer as a function of the energy supplied by the thermal head. Theratio between the magenta and the cyan densities is shown (M/C).

The ratio C/M in Table I and the ratio M/C in Table II are measuredquantities that indicate success in differentially printing one colorrather than another. However, there are two reasons why these numbers donot fully reflect the degree of layer discrimination. First, themeasured densities have a contribution resulting from absorption oflight by the underlying media substrate. (For example, even in theabsence of printing there is a residual absorption of 0.04 densityunits.) Second, each of the dyes has some absorption outside of its owncolor band. Therefore, the ratio of measured cyan and magenta opticaldensities is not the same as the ratio of colorized cyan dye tocolorized magenta dye.

An approximate correction for substrate absorption may be made bysubtracting the optical density of the unheated media from each of themeasured density values. Correcting for the out-of-band absorption ofeach of the dyes is more complicated. Here there is considered athree-color imaging member (comprised of three dye layers) as a generalexample for the correction procedure,

First, the out-of-band absorption was characterized by measuring thedensity of each of the three dyes in each of the three color bands, andcorrecting the densities for the substrate density. Three monochromesamples were used, and each had a particular area-concentration a_(j) ⁰of one of the dyes, where j=C, M or Y depending on whether the dye wascyan, magenta or yellow, respectively.

The results of such a measurement were:

Magenta Yellow Cyan Dye Dye Dye Cyan 0.75 0.02 0.00 Density Magenta 0.260.63 0.04 Density Yellow 0.14 0.11 0.38 Density

The densities recorded in this matrix will be denoted d_(ij), where iand j are the color values C, M and Y, and for example the value d_(CM)is the magenta density of the cyan dye sample

If we have colorized dyes of area-concentration other than that at whichthese data were recorded, then the densities for that dye will scale inproportion to the area-concentration. In particular, if a sample hasarea concentrations a_(C), a_(M), and a_(Y) of colorized cyan, magentaand yellow dye, then under the same printing conditions we will observemeasured densities D_(C), D_(M) and D_(Y) of

D _(C)=(a _(C) /a _(C) ⁰)d _(CC)+(a _(M) /a _(M) ⁰)d _(MC)+(a _(Y) /a_(Y) ⁰)d _(YC)

D _(M)=(a _(C) /a _(C) ⁰)d _(CM)+(a _(M) /a _(M) ⁰)d _(MM)+(a _(Y) /a_(Y) ⁰)d _(YM)

D _(Y)=(a _(C) /a _(C) ⁰)d _(CY)+(a _(M) /a _(M) ⁰)d _(MY)+(a _(Y)/_(Y)⁰)d _(YY)

This can be written in standard matrix notation in the following way:

$\begin{pmatrix}D_{C} \\D_{M} \\D_{Y}\end{pmatrix} = {\begin{pmatrix}d_{CC} & d_{MC} & d_{YC} \\d_{CM} & d_{MM} & d_{YM} \\d_{CY} & d_{MY} & d_{YY}\end{pmatrix}\begin{pmatrix}{a_{C}/a_{C}^{0}} \\{a_{M}/a_{M}^{0}} \\{a_{Y}/a_{Y}^{0}}\end{pmatrix}}$

If the densities D_(C), D_(M) and D_(Y) of a sample are measured, thenwe can use the inverse of this equation to find the area concentrationsof colorized dye in the sample, in comparison to those of thecalibration samples.

$\begin{pmatrix}{a_{C}/a_{C}^{0}} \\{a_{M}/a_{M}^{0}} \\{a_{Y}/a_{Y}^{0}}\end{pmatrix} = {\begin{pmatrix}d_{CC} & d_{MC} & d_{YC} \\d_{CM} & d_{MM} & d_{YM} \\d_{CY} & d_{MY} & d_{YY}\end{pmatrix}^{- 1}\begin{pmatrix}D_{C} \\D_{M} \\D_{Y}\end{pmatrix}}$

These quantities more accurately represent the colorization of eachlayer by the applied heat, and are not confounded by the spectralabsorption overlaps of the dyes in those layers. As such, they moreaccurately represent the degree to which we are able to write on onelayer without affecting another.

We can define “cross-talk” to be the degree to which an attempt toproduce optical density in one color layer alone results in theproduction of undesired optical density in another color layer. Forexample, if we have a medium with a cyan layer and a magenta layer, andwe are attempting to write on the magenta layer, then the relativecross-talk from cyan may be represented by:

${{Cross}\text{-}{talk}} = {\frac{a_{C}*\left( {d_{CC}/a_{C}^{0}} \right)}{a_{M}*\left( {d_{MM}/a_{M}^{0}} \right)} = {\frac{a_{C}/a_{C}^{0}}{a_{M}/a_{M}^{0}}\left( \frac{d_{CC}}{d_{MM}} \right)}}$

An analogous equation can be written for the cross-talk of magenta whenattempting to write on the cyan layer.

These values of cross-talk are recorded in the final column of Tables Iand II. Similar values will be reported for the following examples aswell, but only for cases in which the measured densities are largeenough (density >0.1) to yield meaningful results, and only for layersthat are addressed from the same surface of the imaging member.

TABLE I Energy Cyan Magenta Supplied printed printed Cross-Talk (J/cm²)density density C/M (Magenta) 0.00 0.04 0.04 1.00 0.18 0.04 0.04 1.000.35 0.04 0.04 1.00 0.53 0.04 0.04 1.00 0.71 0.04 0.04 1.00 0.88 0.040.04 1.00 1.06 0.04 0.04 1.00 1.24 0.04 0.04 1.00 1.41 0.04 0.05 0.801.59 0.05 0.05 1.00 1.77 0.06 0.05 1.20 1.94 0.1 0.06 1.67 2.12 0.150.08 1.88 2.29 0.2 0.1 2.00 2.47 0.29 0.12 2.42 0.01 2.65 0.34 0.15 2.270.04 2.82 0.43 0.22 1.95 0.14 3.00 0.5 0.29 1.72 0.22 3.18 0.62 0.351.77 0.22 3.35 0.6 0.42 1.43 0.37 3.53 0.61 0.47 1.30 0.45

TABLE II Energy Cyan Magenta Supplied printed printed Cross-Talk (J/cm²)density density M/C (Cyan) 0 0.04 0.04 1.00 0.30 0.04 0.04 1.00 0.600.04 0.05 1.25 0.90 0.04 0.05 1.25 1.21 0.04 0.05 1.25 1.51 0.04 0.051.25 1.81 0.04 0.05 1.25 2.11 0.04 0.05 1.25 2.41 0.05 0.06 1.20 2.710.05 0.1 2.00 0.14 3.02 0.05 0.15 3.00 0.07 3.32 0.06 0.22 3.67 0.083.62 0.07 0.29 4.15 0.09 3.92 0.09 0.42 4.67 0.10 4.22 0.1 0.54 5.400.09 4.52 0.13 0.69 5.31 0.11 4.83 0.16 0.97 6.06 0.10 5.13 0.22 1.326.00 0.11 5.43 0.26 1.56 6.00 0.12 5.73 0.31 1.69 5.45 0.14 6.03 0.341.74 5.12 0.15

Example II

This example illustrates a two-color imaging member such as isillustrated in FIG. 8. The top color-forming layer produces a yellowcolor, using a unimolecular thermal reaction mechanism as described inU.S. Pat. No. 5,350,870. The lower color-forming layer produces amagenta color, using an acid developer and a magenta leuco dye.

The magenta image-forming layer was prepared as follows:

Dispersions of Leuco Dye I and Acid Developer I were prepared asdescribed in Example I, part A above.

Acid Developer II was dispersed in an aqueous mixture comprising Airvol205 (2% of total solids), Dowfax 2A1 (2% of total solids) and Irganox1035 (5% of total solids) in deionized water, using an attriter equippedwith glass beads and stirred for 24 hours at 10-15° C. The averageparticle size of the resulting dispersion was about 0.52 microns and thetotal solid content was 22.51%.

The above dispersions were used to make the magenta coating fluid inproportions stated below. The coating composition thus prepared wascoated onto Melinex 534 using a Meyer rod, and dried. The intendedcoating thickness was 3 microns.

Ingredient % solids in dried film Leuco Dye I 24.18% Acid Developer I47.49% Acid Developer II 11.63% Joncryl 138 16.16% Zonyl FSN 0.54%

A thermally insulating interlayer was deposited onto the magenta imaginglayer as described in Example I, part B. above, except that the coatingthickness was 16.1 microns.

A yellow image-forming layer was deposited on the thermally insulatinglayer as follows:

Leuco Dye III was dispersed in an aqueous mixture comprising of Airvol205 (4.54% of total solids), Aerosol-OT (2.73% of total solids) andPluronic 25R2 (1.82% of total solids) in deionized water, using anattriter equipped with glass beads and stirred for 18 hours at roomtemperature. The average particle size of the resulting dispersion wasabout 0.49 microns and the total solid content was 25.1%.

The above dispersion was used to make the yellow coating fluid inproportions stated below. The yellow coating composition thus preparedwas coated on the thermally insulating interlayer using a Meyer rod foran intended thickness of 3 microns, and was dried in air.

Ingredient % solids in dried film Leuco Dye III   70% Genflo 3056 22.95%Airvol 205    7% Zonyl FSN  0.05%

A protective overcoat was deposited on the yellow color-forming layer asfollows:

A slip overcoat was coated on the yellow dye layer. The overcoat wasprepared in proportions stated below. The overcoat coating compositionthus prepared was coated on the yellow dye layer using a Meyer rod foran intended thickness of 1.0 micron, and was dried in air.

Ingredient % solids in dried film Glyoxal 8.39% Hymicron ZK-349 31.77%Kiebosol 30R 25 23.77% Zonyl FSA 0.92% Zonyl FSN 3.22% Airvol 540 31.93%

The resulting four-layer imaging member was printed using a laboratorytest-bed printer equipped with a thermal head, model KST-87-12 MPC8(Kyocera Corporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan).The following printing parameters were used:

Printhead width: 3.41 inchPixels per inch: 300Resistor size: 69.7×80 microns

Resistance: 3536 Ohm

Line Speed: 8 milliseconds per linePrint speed: 0.42 inches per secondPressure: 1.5-2 lb/linear inchDot pattern: Rectangular grid.

The yellow layer was printed with a high power/short time condition. Inorder to obtain gradations of color, the pulse width was increased fromzero to a maximum of 1.65 milliseconds (about 20.6% of the total linetime) in twenty-one equal steps, while the voltage supplied to the printhead was maintained at 29.0V.

A lower power/longer time condition was used to print the magenta layer.The pulse width was increased from zero to the 99.5% of the 8millisecond line time in twenty-one equal steps, while the voltagesupplied to the print head was maintained at 16V.

Following printing, the reflection density in each of the printed areaswas measured using a Gretag Macbeth spectrophotometer. The results areshown in Tables III and IV. Table III shows the printing of the yellowlayer as a function of energy supplied by the thermal head. The magentadensities obtained are shown as well. Also included in Table III are theratio between the yellow and the magenta density (Y/M) and thecross-talk. Similarly, Table IV shows the printing of the magenta layeras a function of the energy supplied by the thermal head. The ratiobetween the magenta and the yellow densities is shown (M/Y) as well asthe cross-talk.

TABLE III Energy Yellow Magenta Supplied printed printed Cross-Talk(J/cm²) density density Y/M (Magenta) 0.00 0.07 0.09 0.78 0.26 0.07 0.090.78 0.52 0.06 0.09 0.67 0.78 0.06 0.09 0.67 1.04 0.06 0.09 0.67 1.300.07 0.09 0.78 1.56 0.06 0.09 0.67 1.82 0.06 0.09 0.67 2.08 0.08 0.090.89 2.34 0.11 0.10 1.10 2.60 0.17 0.10 1.70 2.86 0.24 0.11 2.18 0.013.12 0.34 0.12 2.83 0.01 3.38 0.48 0.14 3.43 0.02 3.64 0.58 0.16 3.630.03 3.90 0.68 0.19 3.58 0.06 4.16 0.83 0.23 3.61 0.08 4.41 0.94 0.263.62 0.09 4.67 1.08 0.32 3.38 0.13 4.93 1.13 0.38 2.97 0.18 5.19 1.190.40 2.98 0.18

TABLE IV Energy Magenta Yellow Supplied printed printed Cross-Talk(J/cm²) density density M/Y (Yellow) 0.00 0.10 0.08 1.25 0.38 0.10 0.091.11 0.76 0.10 0.09 1.11 1.15 0.10 0.09 1.11 1.53 0.10 0.08 1.25 1.910.10 0.08 1.25 2.29 0.10 0.07 1.43 2.67 0.10 0.07 1.43 3.05 0.10 0.071.43 3.44 0.10 0.09 1.11 3.82 0.10 0.08 1.25 4.20 0.11 0.08 1.38 4.580.14 0.1 1.40 4.96 0.23 0.13 1.77 5.35 0.40 0.18 2.22 0.22 5.73 0.610.25 2.44 0.17 6.11 0.88 0.34 2.59 0.17 6.49 1.17 0.44 2.66 0.17 6.871.42 0.53 2.68 0.17 7.26 1.65 0.65 2.54 0.20 7.64 1.68 0.74 2.27 0.26

Example III

This example illustrates a two-color imaging member such as isillustrated in FIG. 8 and further including an overcoat layer depositedon the cyan color-forming layer. In this example, thethermally-insulating layer 18 of FIG. 8 is opaque, while the substrate12 is transparent. It is therefore possible, using the imaging memberdescribed in this example, to print both sides of an opaque imagingmember independently, using a thermal head located on only one side ofthe imaging member.

Dispersions of Leuco Dye I and Acid Developer I were prepared asdescribed in Example IV, part C below.

Acid Developer II was dispersed as described above in Example II, partA.

The above dispersions were used to make the magenta coating fluid inproportions stated below. The coating composition thus prepared wascoated onto clear polyester film base (Cronar 412), and dried. Theintended coating coverage was 3.3 g/m².

Ingredient % solids in dried film Leuco Dye I 21.91% Acid Developer I52.71% Airvol 205 14.35% Acid Developer II 10.54% Zonyl FSN 0.49%

A thermally insulating interlayer was deposited onto the magenta imaginglayer as follows:

A coating fluid for the interlayer was prepared in proportions statedbelow. The image interlayer coating composition thus prepared was coatedon the magenta imaging layer for an intended thickness of 8.95 microns.

Ingredient % solids in dried film Glascol C44 99.50% Zonyl FSA 0.50%

An opaque layer was deposited onto the thermally-insulating layer asfollows:

A dispersion of titanium dioxide was prepared as follows:

Titanium dioxide was dispersed in an aqueous mixture comprising Tamol731 (3.86% of total solids), Ludox HS40 (3.85% of total solids) and atrace amount (750 ppm) of Nipa Proxel in deionized water, using anattriter equipped with glass beads and stirred for 18 hours at roomtemperature. The total solid content of the dispersion was 50.2%.

The dispersion so prepared was used to make a coating fluid in theproportions shown below. The coating fluid was coated onto thethermally-insulating layer for an intended thickness of 12.4 microns.

Ingredient % solids in dried film Titanium Dioxide 81.37% Joncryl 13818.08% Zonyl FSN 0.54%

Cyan image-forming layers D1-D3 were deposited on the thermallyinsulating layer as follows:

D1 Cyan developer layer.

Acid Developer III was dispersed as described in Example IV, part E1below.

The above dispersion was used to make the cyan developer coating fluidin proportions stated below. The cyan developer coating composition thusprepared was coated on top of the imaging interlayer for an intendedthickness of 1.74 microns.

Ingredient % solids in dried film Acid Developer III 80.84% Joncryl 13818.54% Zonyl FSN 0.62%

D2 Cyan interlayer.

A cyan interlayer coating fluid was prepared in proportions statedbelow. The cyan interlayer coating composition thus prepared was coatedon top of the cyan developer layer for an intended thickness of 1.0microns.

Ingredient % solids in dried film Airvol 205 99.00% Zonyl FSN 1.00%

D3 Cyan dye layer.

The leuco cyan dye, Dye II, was dispersed as described in Example 4,part E3 below.

The dispersion was used to make the cyan coating fluid in proportionsstated below. The cyan coating composition thus prepared was coated onthe cyan interlayer for an intended thickness of 0.65 microns.

Ingredient % solids in dried film Dye II 59.30% Joncryl 138 39.37% ZonylFSN 1.33%

A protective overcoat was deposited on the cyan color-forming layers asfollows:

A slip overcoat was coated on the cyan dye layer. The overcoat wasprepared in proportions stated in Table VI. The overcoat coatingcomposition thus prepared was coated on the cyan dye layer for anintended thickness of 1.1 micron.

Ingredient % solids in dried film Hymicron ZK-349 31.77% Klebosol 30V-2523.77% Airvol 540 31.93% Glyoxal 8.39% Zonyl FSA 0.92% Zonyl FSN 3.22%

The resulting imaging member was printed as described in Example IIabove. The cyan image was visible from the front of the substrate, whilethe magenta image was visible from the rear. Therefore, opticaldensities for the cyan image were obtained from the top surface of theimaging member, and optical densities for the magenta image from therear of the imaging member.

The cyan layer was printed with a high power/short time condition. Inorder to obtain gradations of color, the pulse width was increased fromzero to a maximum of 1.41 milliseconds (about 18.5% of the total linetime) in twenty equal steps, while the voltage supplied to the printhead was maintained at 29.0V.

A lower power/longer time condition was used to print the magenta layer.The pulse width was increased from zero to the full 8 millisecond linetime in twenty equal steps, while the voltage supplied to the print headwas maintained at 14.5V.

Following printing, the reflection density in each of the printed areaswas measured using a Gretag Macbeth spectrophotometer. The results areshown in Tables V and VI. Table V shows the printing of the cyan layeras a function of energy supplied by the thermal head. The magentadensities obtained are shown as well. Also included in Table V are theratio between the cyan and the magenta density (C/M) and the cross-talk.Similarly, Table VI shows the printing of the magenta layer as afunction of the energy supplied by the thermal head. The ratio betweenthe magenta and the cyan densities is shown (M/C), as well as thecross-talk.

TABLE V Energy Cyan Magenta Supplied printed printed Cross-Talk (J/cm²)density density C/M (Magenta) 0.00 0.08 0.08 1.00 0.23 0.08 0.08 1.000.47 0.08 0.08 1.00 0.70 0.08 0.08 1.00 0.93 0.08 0.08 1.00 1.17 0.080.08 1.00 1.40 0.08 0.08 1.00 1.64 0.08 0.08 1.00 1.87 0.08 0.09 0.892.10 0.08 0.08 1.00 2.34 0.09 0.09 1.00 2.57 0.09 0.09 1.00 2.80 0.10.09 1.11 3.04 0.11 0.10 1.10 3.27 0.13 0.10 1.30 3.51 0.22 0.13 1.690.03 3.74 0.27 0.15 1.80 0.04 3.97 0.35 0.18 1.94 0.04 4.21 0.36 0.201.80 0.10 4.44 0.42 0.24 1.75 0.15 4.67 0.51 0.28 1.82 0.14

TABLE VI Energy Cyan Magenta Supplied printed printed Cross-Talk (J/cm²)density density M/C (Cyan) 0.00 0.08 0.11 1.38 0.31 0.08 0.11 1.38 0.630.08 0.11 1.38 0.94 0.08 0.11 1.38 1.25 0.08 0.11 1.38 1.57 0.08 0.111.38 1.88 0.08 0.11 1.38 2.20 0.08 0.11 1.38 2.51 0.08 0.11 1.38 2.820.08 0.11 1.38 3.14 0.08 0.11 1.38 3.45 0.08 0.11 1.38 3.76 0.08 0.111.38 4.08 0.08 0.12 1.50 4.39 0.09 0.12 1.33 4.70 0.09 0.13 1.44 5.020.10 0.18 1.80 0.27 5.33 0.12 0.25 2.08 0.27 5.65 0.13 0.36 2.77 0.185.96 0.16 0.59 3.69 0.14 6.27 0.19 0.76 4.00 0.14

Example IV

A three-color imaging member such as is illustrated in FIG. 9 andfurther including an overcoat layer deposited on the cyan color-forminglayer was prepared as follows:

A yellow image-forming layer was prepared as follows:

A leuco yellow dye, Leuco Dye IV, was dispersed by a method analogous tothat used to provide the dispersion of Leuco Dye I in part C., below, togive a dye concentration of 20.0%.

Acid Developer IV (10 g) was dispersed in an aqueous mixture comprisingTamol 731 (7.08 g of a 7.06% aqueous solution) and deionized water,32.92 grams, in a 4 ounce glass jar containing 10 grams Mullite beads,stirred for 16 hours at room temperature. The developer concentrationwas 20.0%.

The above dispersions were used to make the yellow coating fluid inproportions stated below. The coating composition thus prepared wascoated onto Melinex 534, and dried. The intended coating coverage was2.0 g/m².

Ingredient % solids in dried film Leuco Dye IV 41.44% Acid Developer IV41.44% Joncryl 138 16.57% Zonyl FSN 0.55%

A thermally insulating interlayer was deposited onto the yellow imaginglayer as follows:

A coating fluid for the interlayer was prepared in proportions stated inTable II. The image interlayer coating composition thus prepared wascoated on the yellow imaging layer for an intended coverage of 9.0 g/m².

Ingredient % solids in dried film Glascol C44 99.50% Zonyl FSA 0.50%

The magenta image-forming layer was prepared as follows:

Leuco Dye I (15.0 g) was dispersed in an aqueous mixture comprisingAirvol 205 (3.38 g of a 20% aqueous solution), Triton X-100 (0.6 g of a5% aqueous solution), and Aerosol-OT (15.01 g of a 19% aqueous solution)in deionized water (31.07 g), in a 4 ounce glass jar containing Mullitebeads, stirred for 16 hours at room temperature. The total dye contentwas 20.00%.

Acid developer I (10 g) was dispersed in an aqueous mixture comprisingTamol 731 (7.08 g of a 7.06% aqueous solution) and deionized water,32.92 grams, in a 4 ounce glass jar containing 10 grams Mullite beads,stirred for 16 hours at room temperature. The developer concentrationwas 20.0%.

Acid developer II was dispersed as described above in Example II, partA.

The above dispersions were used to make the magenta coating fluid inproportions stated below. The coating composition thus prepared wascoated onto the thermally-insulating interlayer, and dried. The intendedcoating coverage was 1.67 g/m².

Ingredient % solids in dried film Leuco Dye I 24.18% Acid Developer I47.50% Joncryl 138 16.16% Acid Developer II 11.63% Zonyl FSN 0.54%

A thermally insulating interlayer was deposited onto the magenta imaginglayer as follows:

A coating fluid for the interlayer was prepared in proportions statedbelow. The image interlayer coating composition thus prepared was coatedon the magenta imaging layer in three passes, for an intended coverageof 13.4 g/m².

Ingredient % solids in dried film Glascol C44 99.50% Zonyl FSA 0.50%

Cyan image-forming layers E1-E3 were deposited on thethermally-insulating layer as follows:

E1 Cyan developer layer.

Acid developer III (10 g) was dispersed in an aqueous mixture comprisingTamol 731 (7.08 g of a 7.06% aqueous solution) and deionized water,32.92 grams, in a 4 ounce glass jar containing 10 grams Mullite beads,stirred for 16 hours at room temperature. The developer concentrationwas 20.0%.

The above dispersion was used to make the cyan developer coating fluidin proportions stated below. The cyan developer coating composition thusprepared was coated on top of the thermally-insulating interlayer for anintended thickness of 1.94 g/m².

Ingredient % solids in dried film Acid Developer III 89.5% Joncryl 1389.5% Zonyl FSN 1.0%

E2 Cyan interlayer.

A cyan interlayer coating fluid was prepared in proportions statedbelow. The cyan interlayer coating composition thus prepared was coatedon top of the cyan developer layer for an intended thickness of 1.0g/m².

Ingredient % solids in dried film Airvol 205 99.00% Zonyl FSN 1.00%

E3 Cyan dye layer.

Leuco Dye II (15.0 g) was dispersed in an aqueous mixture comprisingAirvol 350 (11.06 g of a 9.5% aqueous solution), Airvol 205 (2.25 g of a20% aqueous solution), Aerosol-OT (2.53 g of a 19% aqueous solution) andTriton X-100 (1.49 g of a 5% aqueous solution) in deionized water (52.61g) in a 4 ounce glass jar containing Mullite beads, stirred for 16 hoursat room temperature. The dye concentration was 20.0%.

The above dispersion was used to make the cyan coating fluid inproportions stated below. The cyan coating composition thus prepared wascoated on the cyan interlayer for an intended coverage of 0.65 g/m².

Ingredient % solids in dried film Leuco Dye II 59.30% Joncryl 138 39.37%Zonyl FSN 1.33%

A protective overcoat was deposited on the cyan color-forming layers asfollows:

A slip overcoat was coated on the cyan dye layer. The overcoat wasprepared in proportions stated below. The overcoat coating compositionthus prepared was coated on the cyan dye layer for an intended coverageof 1.1 g/m².

Ingredient % solids in dried film Hymicron ZK-349 31.77% Klebosol 30V-2523.77% Airvol 540 31.93% Glyoxal 8.39% Zonyl FSA 0.92% Zonyl FSN 3.22%

The resulting imaging member was printed using a laboratory test-bedprinter equipped with a thermal head, model KST-87-12 MPC8 (KyoceraCorporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan). Thefollowing printing parameters were used:

Printhead width: 3.41 inchPixels per inch: 300Resistor size: 69.7×80 microns

Resistance: 3536 Ohm

Line Speed: 8 milliseconds per linePrint speed: 0.42 inches per secondPressure: 1.5-2 lb/linear inchDot pattern: Rectangular grid.

The cyan layer was printed with a high power/short time condition. Inorder to obtain gradations of color, the pulse width was increased fromzero to a maximum of 1.31 milliseconds (about 16.4% of the total linetime) in ten equal steps, while the voltage supplied to the print headwas maintained at 29.0V.

A lower power/longer time condition was used to print the magenta layer.The pulse width was increased from zero to the 99.5% of the 8millisecond line time in ten equal steps, while the voltage supplied tothe print head was maintained at 15V.

A very low power/very long time was used to print the yellow layer. Someof the printing conditions were changed, as follows:

Line Speed: 15.23 milliseconds per linePulse width: 15.23 millisecondsPrint speed: 0.0011 inches per secondLines printed: 1600, one step of maximum density.

Following printing, the reflection density in each of the printed areaswas measured using a Gretag Macbeth spectrophotometer. The results areshown in Tables VII, VIII and IX. Table VII shows the printing of thecyan layer as a function of energy supplied by the thermal head. Themagenta and yellow densities and cross-talk obtained are shown as well.Similarly, Table VIII shows the printing of the magenta layer as afunction of the energy supplied by the thermal head. Table IX shows thedensity obtained when printing the yellow layer as a function of appliedvoltage and energy.

TABLE VII Cyan Magenta Yellow Cross- Cross- printed printed printed TalkTalk density density density (Magenta) (Yellow) 0.00 0.06 0.07 0.17 0.410.06 0.07 0.17 0.83 0.06 0.07 0.17 1.24 0.05 0.07 0.16 1.65 0.06 0.070.16 2.07 0.06 0.07 0.18 2.48 0.07 0.08 0.19 2.89 0.12 0.09 0.19 −0.030.15 3.30 0.19 0.12 0.21 0.03 0.12 3.72 0.19 0.14 0.22 0.18 0.17 4.130.33 0.17 0.24 0.02 0.07

TABLE VIII Energy Cyan Magenta Yellow Cross- Cross- Supplied printedprinted printed Talk Talk (J/cm²) density density density (Cyan)(Yellow) 0.00 0.05 0.07 0.16 0.67 0.05 0.07 0.16 1.34 0.05 0.07 0.172.01 0.05 0.07 0.18 2.68 0.06 0.07 0.18 3.36 0.06 0.08 0.18 4.03 0.080.12 0.19 4.70 0.08 0.24 0.22 0.16 0.17 5.37 0.10 0.38 0.25 0.14 0.116.04 0.16 0.63 0.33 0.18 0.12 6.71 0.20 0.91 0.42 0.16 0.13

TABLE IX Voltage Energy Cyan Magenta Yellow applied Supplied printedprinted printed (V) (J/cm²) density density density 7.5 639 0.06 0.260.73 7 557 0.06 0.23 0.70

This example shows that all three colors may be printed independentlyusing a thermal head addressing the same side of an imaging memberconstructed as shown in FIG. 9.

Example V

This example illustrates a three color imaging member such asillustrated in FIG. 10. The top image-forming layer produces a yellowcolor, using a unimolecular thermal reaction mechanism as described inU.S. Pat. No. 5,350,870. The middle image-forming layer produces amagenta color, using an acid developer, an acid co-developer, and amagenta leuco dye. The bottom image-forming layer produces a cyan color,using an acid developer, and a cyan leuco dye. In between the magentaand cyan layer, a thick clear poly(ethylene terephthalate) film base ofapproximately 102 micron thickness (Cronar 412) was used. Below thebottom cyan image-forming layer, a thick, opaque, white layer was usedas a masking layer. The imaging member was addressed from the top(yellow and magenta) and the bottom (cyan). Because of the presence ofthe opaque layer, however, all three colors were visible only from thetop. In this manner, a full-color image could be obtained.

The magenta image-forming layer was prepared as follows:

Dispersions of Leuco Dye I and Acid Developer I were prepared asdescribed in Example I, part A. above.

A dispersion of Acid Developer III was prepared as described in ExampleII, part A. above.

The above dispersions were used to make the magenta coating fluid inproportions stated below. The coating composition thus prepared wascoated on a clear poly(ethylene terephthalate) film base ofapproximately 102 microns' thickness (Cronar 412) onto thegelatine-subcoated side, using a Meyer rod, and dried. The intendedcoating thickness was 3 microns.

Ingredient % solids in dried film Leuco Dye I 24.18% Acid Developer I47.49% Acid Developer III 11.63% Jonyl 138 16.16% Zonyl FSN 0.54%

A thermally insulating interlayer was deposited onto the magenta imaginglayer as described in Example II, part B. above.

A yellow image-forming layer was deposited on the thermally insulatinglayer as follows:

A dispersion of Leuco Dye III was prepared as described in Example II,part C. above. This dispersion was used to make the yellow coating fluidin proportions stated below. The yellow coating composition thusprepared was coated on the thermally insulating interlayer using a Meyerrod for an intended thickness of 3 microns, and was dried in air.

Ingredient % solids in dried film Leuco Dye III   70% Genflo 3056 22.95%Airvol 205    7% Zonyl FSN  0.05%

A protective overcoat was deposited on the yellow image-forming layersas follows:

A slip overcoat was coated on the yellow dye layer. The overcoat wasprepared in proportions stated below. The overcoat coating compositionthus prepared was coated on the yellow dye layer using a Meyer rod foran intended thickness of 1.0 microns, and was dried in air.

Ingredient % solids in dried film Glyoxal 8.39% Hymicron ZK-349 31.77%Klebosol 30V-25 23.77% Zonyl FSA 0.92% Zonyl FSN 3.22% Airvol 540 31.93%

The cyan image-forming layer was prepared as follows:

Leuco Dye II was dispersed in an aqueous mixture comprising Airvol 205(2.7% of total solids), Airvol 350 (6.3% of total solids), Triton X-100(0.18% of total solids) and Aerosol-OT (0.9% of total solids) indeionized water, using an attriter equipped with glass beads and stirredfor 18 hours at room temperature. The total solid content of thedispersion was 20%.

A dispersion of Acid Developer I was prepared as described in Example I,part A. above.

The above dispersions were used to make the cyan coating fluid inproportions stated below. The coating composition thus prepared wascoated onto the opposite side of the clear poly(ethylene terephthalate)film base as coatings A-D, using a Meyer rod, and dried in air. Theintended coating thickness was 2 microns.

Ingredient % solids in dried film Leuco Dye II 28.38% Acid Developer I41.62% GenFlo 3056 22.90% Airvol 205    7% Zonyl FSN  0.1%

The Masking, Opaque Layer.

Titanium dioxide was dispersed in an aqueous mixture comprising Tamol731 (3.86% of total solids), Ludox HS40 (3.85% of total solids) and atrace amount (750 ppm) of Nipa Proxel in deionized water, using anattriter equipped with glass beads and stirred for 18 hours at roomtemperature. The total solid content of the dispersion was 50.2%.

The above dispersion was used to make a coating fluid in proportionsstated below. The coating composition thus prepared was coated on thecyan image-forming layer using a Meyer rod for an intended thickness of15 micron, and was dried in air.

Ingredient % solids in dried film Titanium dioxide 81.37% Joncryl 13818.08% Zonyl FSN 0.54%

A protective overcoat was deposited on the opaque layer as described inpart D. above.

The resulting imaging member was printed using a laboratory test-bedprinter equipped with a thermal head, model KST-87-12 MPC8 (KyoceraCorporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan). Thefollowing printing parameters were used:

Printhead width: 3.41 inchPixels per inch: 300Resistor size: 69.7×80 microns

Resistance: 3536 Ohm

Line Speed: 8 milliseconds per linePrint speed: 0.42 inches per secondPressure: 1.5-2 lb/linear inchDot pattern: Rectangular grid.

The yellow layer was printed from the front side with a high power/shorttime condition. In order to obtain gradations of color, the pulse widthwas increased from zero to a maximum of 1.65 milliseconds (about 20.6%of the total line time) in twenty-one equal steps, while the voltagesupplied to the print head was maintained at 29.0V.

A lower power/longer time condition was used to print the magenta layer,which was also addressed from the front side. The pulse width wasincreased from zero to the 99.5% of 8 millisecond line time intwenty-one equal steps, while the voltage supplied to the print head wasmaintained at 16V.

The cyan layer was printed with a high power/short time condition fromthe backside (the side of the film base bearing the opaque layer). Inorder to obtain gradations of color, the pulse width was increased fromzero to a maximum of 1.65 milliseconds (about 20.6% of the total linetime) in twenty-one equal steps, while the voltage supplied to the printhead was maintained at 29.0V.

Following printing, the reflection density in each of the printed areaswas measured using a Gretag Macbeth spectrophotometer. The results areshown in Tables X, XI and XII. Table X shows the printing of the yellowlayer as a function of energy supplied by the thermal head. The magentaand cyan densities obtained are shown as well. Also included in Table Xare the ratio between the yellow and the magenta density (Y/M) and thecross-talk. Similarly, Table XI shows the printing of the magenta layeras a function of the energy supplied by the thermal head. The ratiobetween the magenta and the yellow densities is shown (M/Y) as well asthe cross-talk. In Table XII, printing of cyan layer as a function ofthe energy supplied by the thermal head is also listed. The ratiobetween the cyan and magenta densities is shown (C/M).

TABLE X Energy Yellow Magenta Cyan Cross- Supplied printed printedprinted Talk (J/cm²) density density density Y/M (Magenta) 0.00 0.110.11 0.08 1.00 0.26 0.11 0.11 0.08 1.00 0.52 0.11 0.11 0.08 1.00 0.780.12 0.11 0.08 1.09 1.04 0.11 0.11 0.08 1.00 1.30 0.11 0.11 0.08 1.001.56 0.12 0.11 0.08 1.09 1.82 0.12 0.11 0.08 1.09 2.08 0.13 0.11 0.081.18 2.34 0.15 0.11 0.08 1.36 2.60 0.21 0.12 0.08 1.75 −0.01 2.86 0.280.12 0.08 2.33 −0.05 3.12 0.36 0.13 0.08 2.77 −0.03 3.38 0.46 0.15 0.083.07 0.01 3.64 0.63 0.17 0.08 3.71 0.01 3.90 0.79 0.20 0.08 3.95 0.034.16 0.98 0.24 0.08 4.08 0.05 4.41 1.12 0.27 0.08 4.15 0.06 4.67 1.240.30 0.09 4.13 0.06 4.93 1.36 0.33 0.09 4.12 0.07 5.19 1.44 0.36 0.094.00 0.08

TABLE XI Energy Magenta Yellow Cyan Cross- Supplied printed printedprinted Talk (J/cm²) density density density M/Y (Yellow) 0.00 0.11 0.110.07 1.00 0.38 0.11 0.11 0.08 1.00 0.76 0.11 0.11 0.07 1.00 1.15 0.110.11 0.08 1.00 1.53 0.11 0.11 0.08 1.00 1.91 0.11 0.11 0.08 1.00 2.290.11 0.11 0.08 1.00 2.67 0.11 0.11 0.07 1.00 3.05 0.11 0.11 0.07 1.003.44 0.11 0.12 0.07 0.92 3.82 0.11 0.12 0.07 0.92 4.20 0.12 0.13 0.070.92 4.58 0.13 0.14 0.07 0.93 4.96 0.17 0.16 0.07 1.06 5.35 0.24 0.190.08 1.26 0.47 5.73 0.39 0.25 0.09 1.56 0.34 6.11 0.60 0.34 0.10 1.760.31 6.49 0.86 0.44 0.12 1.95 0.28 6.87 1.16 0.55 0.13 2.11 0.25 7.261.50 0.71 0.15 2.11 0.27 7.64 1.54 0.81 0.16 1.90 0.33

TABLE XII Energy Magenta Yellow Supplied Cyan printed printed printed(J/cm²) density density density C/M 0.00 0.07 0.11 0.11 0.64 0.26 0.070.11 0.11 0.64 0.52 0.07 0.11 0.11 0.64 0.78 0.07 0.11 0.11 0.64 1.040.07 0.11 0.11 0.64 1.30 0.07 0.11 0.11 0.64 1.56 0.07 0.11 0.11 0.641.82 0.07 0.11 0.11 0.64 2.08 0.07 0.11 0.11 0.64 2.34 0.07 0.11 0.110.64 2.60 0.08 0.11 0.11 0.73 2.86 0.10 0.11 0.11 0.91 3.12 0.16 0.130.12 1.23 3.38 0.24 0.15 0.13 1.60 3.64 0.33 0.17 0.14 1.94 3.90 0.430.21 0.15 2.05 4.16 0.57 0.26 0.18 2.19 4.41 0.90 0.42 0.27 2.14 4.671.09 0.53 0.33 2.06 4.93 1.06 0.52 0.33 2.04 5.19 1.03 0.51 0.32 2.02

Example VI

This example illustrates a three color imaging member such asillustrated in FIG. 10. The top image-forming layer produces a cyancolor, the middle image-forming layer produces a magenta color, and thebottom image-forming layer produces a yellow color. All three layers usean acid developer or developers, and a leuco dye. In between the magentaand yellow layers, a thick clear poly(ethylene terephthalate) film baseof approximately 102 micron thickness (Cronar 412) was used. Below thebottom yellow image-forming layer, a thick, opaque, white layer was usedas a masking layer. The imaging member was addressed from the top (cyanand magenta) and the bottom (yellow). Because of the presence of theopaque layer, however, all three colors were visible only from the top.In this manner, a full-color image could be obtained.

The magenta color-forming layer was prepared as follows:

Dispersions of Leuco Dye I and Acid Developer I were prepared asdescribed in Example IV, part C above. A dispersion of Acid Developer IIwas prepared as described in Example II, part A above.

The above dispersions were used to make the magenta coating fluid inproportions stated below. The coating composition thus prepared wascoated onto Cronar 412, and dried. The intended coating coverage was 2.0g/m².

Ingredient % solids in dried film Leuco Dye I 24.18% Acid Developer I47.50% Joncryl 138 16.16% Acid Developer II 11.63% Zonyl FSN 0.54%

A thermally insulating interlayer was deposited onto the magenta imaginglayer as follows:

A coating fluid for the interlayer was prepared in proportions statedbelow. The image interlayer coating composition thus prepared was coatedon the magenta imaging layer in three passes, for an intended coverageof 13.4 g/m².

Ingredient % solids in dried film Glascol C44 99.50% Zonyl FSA 0.50%

Cyan image-forming layers C1-C3 were deposited on the thermallyinsulating layer as follows:

C1 Cyan developer layer.

A dispersion of Acid Developer III was prepared as described in ExampleIV, part E1 above.

The above dispersion was used to make the cyan developer coating fluidin proportions stated below.

The cyan developer coating composition thus prepared was coated on topof the thermally-insulating interlayer for an intended thickness of 2.1g/m², and was dried.

Ingredient % solids in dried film Joncryl 138 10.0% Acid Developer III89.5% Zonyl FSN 0.50%

C2 Cyan interlayer.

A cyan interlayer coating fluid was prepared in proportions statedbelow. The cyan interlayer coating composition thus prepared was coatedon top of the cyan developer layer for an intended thickness of 1.0g/m².

Ingredient % solids in dried film Airvol 205 99.00% Zonyl FSN 1.00%

C3 Cyan dye layer.

Leuco dye II was dispersed as described in Example IV, part E3 above.

The above dispersion was used to make the cyan coating fluid inproportions stated below. The cyan coating composition thus prepared wascoated on the cyan interlayer for an intended coverage of 0.65 g/m².

Ingredient % solids in dried film Leuco Dye II 59.30% Joncryl 138 39.37%Zonyl FSN 1.33%

A protective overcoat was deposited on the cyan image-forming layers asfollows:

A slip overcoat was coated on the cyan dye layer. The overcoat wasprepared in proportions stated below. The overcoat coating compositionthus prepared was coated on the cyan dye layer for an intended coverageof 1.1 g/m².

Ingredient % solids in dried film Hymicron ZK-349 31.77% Klebosol 30V-2523.77% Airvol 540 31.93% Glyoxal 8.39% Zonyl FSA 0.92% Zonyl FSN 3.22%

A yellow image-forming layer was deposited onto the reverse of the clearsubstrate using the procedure described in Example IV, part A above,except that the dried coverage was 1.94 g/m².

A white, opaque layer was deposited onto the yellow color-forming layeras follows:

A dispersion of titanium dioxide was prepared as described in Example V,part F. above.

A coating fluid was prepared from the dispersion so formed inproportions stated below. The coating composition thus prepared wascoated on top of the yellow color-forming layer for an intended coverageof 10.76 g/m².

Ingredient % solids in dried film Titanium dioxide 89.70% Joncryl 1389.97% Zonyl FSN 0.33%

A protective overcoat was deposited on the opaque layer as described inpart D. above.

The resulting imaging member was printed using a laboratory test-bedprinter equipped with a thermal head, model KST-87-12 MPC8 (KyoceraCorporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan). Thefollowing printing parameters were used:

Printhead width: 3.41 inchPixels per inch: 300Resistor size: 69.7×80 microns

Resistance: 3536 Ohm

Line Speed: 8 milliseconds per linePrint speed: 0.42 inches per secondPressure: 1.5-2 lb/linear inchDot pattern: Rectangular grid.

The cyan layer was printed from the front side with a high power/shorttime condition. In order to obtain gradations of color, the pulse widthwas increased from zero to a maximum of 1.25 milliseconds (about 16.4%of the total line time) in twenty-one equal steps, while the voltagesupplied to the print head was maintained at 29.0V.

A lower power/longer time condition was used to print the magenta layer,which was also addressed from the front side. The pulse width wasincreased from zero to the 99.5% of 8 millisecond line time intwenty-one equal steps, while the voltage supplied to the print head wasmaintained at 14.5V.

The yellow layer was printed with a lower power/longer time conditionfrom the backside (the side of the film base bearing the opaque layer).The pulse width was increased from zero to the 99.5% of 8 millisecondline time in twenty-one equal steps, while the voltage supplied to theprint head was maintained at 14.5V.

Following printing, the reflection density in each of the printed areaswas measured using a Gretag Macbeth spectrophotometer. The results areshown in Tables XIII, XIV and XV. Table XIII shows the printing of thecyan layer as a function of energy supplied by the thermal head. Themagenta and yellow densities obtained are shown as well. Also includedin Table XIII are the ratio between the cyan and the magenta density(C/M) and the cross-talk. Similarly, Table XIV shows the printing of themagenta layer as a function of the energy supplied by the thermal head.The ratio between the magenta and the cyan densities is shown (M/C) aswell as the cross-talk. In Table XV, printing of yellow layer as afunction of the energy supplied by the thermal head is also listed. Theratio between the yellow and magenta densities is shown (Y/M).

TABLE XIII Energy Cyan Magenta Yellow Cross- Supplied printed printedprinted Talk (J/cm²) density density density C/M (Magenta) 1.57 0.070.10 0.23 0.70 1.83 0.08 0.10 0.23 0.80 2.09 0.08 0.11 0.25 0.73 2.340.08 0.10 0.23 0.80 2.60 0.11 0.11 0.23 1.00 2.85 0.12 0.12 0.23 1.003.11 0.16 0.13 0.24 1.23 −0.01 3.36 0.20 0.14 0.25 1.43 −0.04 3.62 0.260.16 0.26 1.63 −0.03 3.87 0.28 0.17 0.27 1.65 −0.01 4.13 0.36 0.20 0.281.80 0.00

TABLE XIV Energy Magenta Cyan Yellow Cross- Supplied printed printedprinted Talk (J/cm²) density density density M/C (Cyan) 3.14 0.10 0.070.20 1.43 3.45 0.11 0.09 0.22 1.22 3.76 0.11 0.09 0.22 1.22 4.08 0.120.10 0.22 1.20 4.39 0.13 0.10 0.21 1.30 4.70 0.16 0.11 0.23 1.45 5.020.21 0.11 0.24 1.91 0.39 5.33 0.30 0.14 0.24 2.14 0.36 5.65 0.43 0.160.26 2.69 0.27 5.96 0.57 0.17 0.29 3.35 0.20 6.27 0.60 0.18 0.29 3.330.20

TABLE XV Energy Yellow Magenta Cyan Supplied printed printed printed(J/cm²) density density density Y/M 0.00 0.23 0.10 0.07 2.30 0.63 0.230.10 0.07 2.30 1.25 0.24 0.10 0.08 2.40 1.88 0.22 0.10 0.08 2.20 2.510.22 0.10 0.07 2.20 3.14 0.23 0.10 0.08 2.30 3.76 0.32 0.10 0.07 3.204.39 0.57 0.12 0.07 4.75 5.02 0.85 0.18 0.07 4.72 5.65 0.95 0.25 0.073.80 6.27 0.98 0.33 0.08 2.97

Example VII

This example illustrates the preparation of the zinc salt of3-methyl-5-n-octylsalicylic acid.

Preparation of methyl 3-methyl-5-n-octanoyl salicylate

Aluminum chloride (98 g) was suspended in methylene chloride (150 mL) ina 1 L flask and the mixture was cooled to 5° C. in an ice bath. To thestirred mixture was added methyl 3-methylsalicylate (50 g) and octanoylchloride (98 g) in 150 mL of methylene chloride over a 1 hr period. Thereaction was stirred for an additional 30 min. at 5° C. and then at 3hrs at room temperature. The reaction was poured into 500 g of icecontaining 50 mL of concentrated hydrochloric acid. The organic layerwas separated and the aqueous layer extracted twice with 50 mL ofmethylene chloride. The methylene chloride was washed with a saturatedaqueous solution of sodium bicarbonate, dried with magnesium sulfate,filtered, and evaporated to an oil which solidified to 90 g of tancrystals. ¹H and ¹³C NMR spectra were consistent with expected product.

Preparation of 3-methyl-5-n-octanoyl salicylic acid

Methyl 3-methyl-5-n-octanoyl salicylate (prepared as described above, 90g) was dissolved in 200 mL of ethanol and 350 mL of water. To thissolution was added 100 g of a 50% aqueous solution of sodium hydroxideand the solution was than stirred at 85° C. for 6 hrs. The reaction wascooled in an ice bath and a 50% aqueous solution of hydrochloric acidwas slowly added until a pH of 1 was attained. The precipitate wasfiltered, washed with water (5×50 mL) and dried under reduced pressureat 45° C. for 6 hrs. to give 80 g of pale tan product. ¹H and ¹³C NMRspectra were consistent with expected product.

Preparation of 3-methyl-5-n-octyl salicylic acid

16 g of mercury (II) chloride was dissolved in 8 mL of concentratedhydrochloric acid and 200 mL of water in a 1 L flask. 165 g Mossy zincwas shaken with this solution. The water was decanted off and to thezinc was added 240 mL of concentrated hydrochloric acid, 100 mL of waterand 3-methyl-5-n-octanoyl salicylic acid (prepared as described above,80 g). The mixture was refluxed with stirring for 24 hrs. with anadditional 50 mL of concentrated hydrochloric acid being added every 6hrs (3 times). The reaction was decanted hot from the zinc and cooled tosolidify the product. The product was collected by filtration, washedwith (2×100 mL water) and dissolved in 300 mL hot ethanol. 50 mL ofwater was added and the solution was refrigerated to give whitecrystals. The solid was filtered, washed (3×100 mL water) and driedunder reduced pressure at 45° C. for 8 hrs to give 65 g of product. ¹Hand ¹³C NMR spectra were consistent with expected product.

Preparation of 3-methyl-5-n-octyl salicylic acid zinc Salt

3-Methyl-5-n-octyl salicylic acid (prepared as described above, 48 g)was added with stirring to a solution of 14.5 g of a 50% aqueoussolution of sodium hydroxide and 200 mL water in a 4 L beaker. To thiswas added 1 L of water and the solution was heated to 65° C. To the hotsolution was then added with stirring 24.5 g of zinc chloride in 40 mlof water. A gummy solid precipitated. The solution decanted and theremaining solid was dissolved in 300 mL hot 95% ethanol. The hotsolution was diluted with 500 ml of water and refrigerated. The productwas filtered and washed (3×500 mL water) to give 53 g of off-whitesolid.

Example VIII

This example illustrates a three color imaging member with an overcoatlayer deposited on each side, and a method for writing multiple colorson this member in a single pass using two thermal print heads. The topcolor-forming layer produces a yellow color, using a unimolecularthermal reaction mechanism as described in U.S. Pat. No. 5,350,870. Themiddle color-forming layer produces a magenta color, using an aciddeveloper, an acid co-developer, and a magenta leuco dye. The bottomcolor-forming layer produces a cyan color, using an acid developer, anda cyan leuco dye. In between the magenta and cyan layer, a thick clearpoly(ethylene terephthalate) film base of approximately 102 micronthickness (Cronar 412) was used. Below the bottom cyan image-forminglayer, a thick, opaque, white layer was used as a masking layer. Theimaging member was addressed from the top (yellow and magenta) and thebottom (cyan). Because of the presence of the opaque layer, however, allthree colors were visible only from the top. In this manner, afull-color image could be obtained.

The magenta image-forming layer was prepared as follows:

Dispersions of Leuco Dye I and Acid Developer I were prepared asdescribed in Example I, part A. above.

A dispersion of Acid Developer III was prepared as described in ExampleII, part A. above.

The above dispersions were used to make the magenta coating fluid inproportions stated below. The coating composition thus prepared wascoated on a clear poly(ethylene terephthalate) film base ofapproximately 102 microns' thickness (Cronar 412) onto thegelatin-subcoated side, using a Meyer rod, and dried. The intendedcoating thickness was 3.06 microns.

Ingredient % solids in dried film Leuco Dye I 12.08% Acid Developer I28.70% Acid Developer II 15.14% Genflo 3056 37.38% Airvol 205 6.38%Zonyl FSN 0.32%

A thermally insulating interlayer was deposited onto the magenta imaginglayer as follows:

B1. A coating fluid for the interlayer was prepared in the proportionsstated below. The image interlayer coating composition thus prepared wascoated on the imaging layer using a Meyer rod for an intended thicknessof 6.85 microns, and was dried in air.

Ingredient % solids in dried film Glascol C44 99.78% Zonyl FSN 0.22%

B2. A second insulating interlayer of the same description was thencoated on the first interlayer and dried.

B3. Finally, a third insulating interlayer of the same description wascoated on the second interlayer and dried. The combination of the threeinsulating interlayers comprised an insulating layer with an intendedtotal thickness of 20.55 microns.

A yellow image-forming layer was deposited on the third thermallyinsulating layer as follows:

A dispersion of Leuco Dye III was prepared as described in Example II,part C. above. This dispersion was used to make the yellow coating fluidin proportions stated below. The yellow coating composition thusprepared was coated on the thermally insulating interlayer using a Meyerrod for an intended thickness of 3.21 microns, and was dried in air.

Ingredient % solids in dried film Leuco Dye III 49.42% Airvol 205 11.68%Genflo 3056 38.00% Zonyl FSN 0.90%

A protective overcoat was deposited on the yellow image-forming layersas follows:

A slip overcoat was coated on the yellow dye layer. The overcoat wasprepared in proportions stated below. The overcoat coating compositionthus prepared was coated on the yellow dye layer using a Meyer rod foran intended thickness of 1.46 microns, and was dried in air.

Ingredient % solids in dried film Glyoxal 8.54% Hymicron ZK-349 31.95%Klebosol 30V-25 23.89% Zonyl FSA 0.98% Zonyl FSN 2.44% Airvol 540 32.20%

The cyan image-forming layer was prepared as follows:

Leuco Dye II was dispersed in an aqueous mixture comprising Airvol 205(2.7% of total solids), Airvol 350 (6.3% of total solids), Triton X-100(0.18% of total solids) and Aerosol-OT (0.9% of total solids) indeionized water, using an attriter equipped with glass beads and stirredfor 18 hours at room temperature. The total solid content of thedispersion was 20%.

A dispersion of Acid Developer I was prepared as described in Example I,part A. above.

The above dispersions were used to make the cyan coating fluid inproportions stated below. The coating composition thus prepared wascoated onto the opposite side of the clear poly(ethylene terephthalate)film base as coatings A-D, using a Meyer rod, and dried in air. Theintended coating thickness was 3.01 microns.

Ingredient % solids in dried film Leuco Dye II 18.94% Acid Developer I51.08% GenFlo 3056 22.86% Airvol 205 7.01% Zonyl FSN 0.10%

The masking, opaque layer.

Titanium dioxide was dispersed in an aqueous mixture comprising Tamol731 (3.86% of total solids), Ludox HS40 (3.85% of total solids) and atrace amount (750 ppm) of Nipa Proxel in deionized water, using anattriter equipped with glass beads and stirred for 18 hours at roomtemperature. The total solid content of the dispersion was 50.2%.

The above dispersion was used to make a coating fluid in proportionsstated below. The coating composition thus prepared was coated on thecyan image-forming layer using a Meyer rod for an intended thickness of15 micron, and was dried in air.

Ingredient % solids in dried film Titanium dioxide 88.61% Airvol 20511.08% Zonyl FSN 0.32%

A protective overcoat was deposited on the opaque layer as described inpart D. above.

The resulting imaging member was printed using a laboratory test-bedprinter equipped with two thermal heads, model KYT-106-12PAN13 (KyoceraCorporation, 6 Takedatobadono-cho, Fushimi-ku, Kyoto, Japan). Thefollowing printing parameters were used:

Printhead width: 4.16 inchPixels per inch: 300Resistor size: 70×80 microns

Resistance: 3900 Ohm

Line Speed: 10.7 milliseconds per linePrint speed: 0.31 inches per secondPressure: 1.5-2 lb/linear inchDot pattern: Rectangular grid.

The yellow layer was printed from the front side with a high power/shorttime condition. In order to obtain gradations of color, the pulse widthwas increased from zero to a maximum of 1.99 milliseconds (about 18.2%of the total line time) in ten equal steps, while the voltage suppliedto the print head was maintained at 26.5V. Within this pulse width therewere 120 subintervals, and each had a duty cycle of 95%.

A lower power/longer time condition was used to print the magenta layer,which was also addressed from the front side. The pulse width wasincreased from zero to a maximum of 8.5 milliseconds (about 79% of thetotal line time) in 10 equal steps, while the voltage supplied to theprint head was maintained at 26.5V. Within this pulse width, there were525 subintervals, and each had a duty cycle of 30%.

Unlike previous examples, the yellow pulses and magenta pulses wereinterleaved, and were supplied by a single print head in a single pass,so that a single printhead was printing two colors synchronously. Theselection of high power or low power was made by alternating between the95% duty cycle used for printing yellow and the 30% duty cycle used forprinting magenta. The print head voltage was constant at 26.5V.

The cyan layer was printed with a low-power, long-time condition fromthe backside (the side of the film base bearing the opaque TiO₂ layer).In order to obtain gradations of color, the pulse width was increasedfrom zero to a maximum of 10.5 milliseconds (about 98% of the total linetime) in 10 equal steps, while the voltage supplied to the print headwas maintained at 21.0V.

In addition to printing gradations of color for each of the three dyelayers,

gradations of combined pairs of the colors, and of the combination ofall three colors, were printed.

Following printing, the reflection density in each of the printed areaswas measured using a Gretag Macbeth spectrophotometer. Results forwriting on the yellow, magenta and cyan layers are shown in Tables XVI,XVII and XVIII.

Table XVI shows the printing of the cyan layer as a function of energysupplied by the thermal head. The magenta and yellow densities obtainedare shown as well. Similarly, Table XVII shows the printing of themagenta layer as a function of the energy supplied by the thermal head.The ratio between the magenta and the yellow densities is also shown(M/Y) as well as the cross-talk. In Table XVIII, printing of yellowlayer as a function of the energy supplied by the thermal head is alsolisted. The ratio between the yellow and magenta densities is shown(Y/M) as well as the cross-talk.

TABLE XVI Energy Cyan Magenta Yellow Supplied printed printed printed(J/cm²) density density density 1.79 0.10 0.12 0.20 2.07 0.11 0.12 0.202.35 0.11 0.12 0.19 2.63 0.12 0.13 0.19 2.92 0.17 0.13 0.20 3.20 0.250.15 0.20 3.48 0.34 0.18 0.22 3.76 0.56 0.25 0.25 4.05 0.82 0.35 0.294.33 1.07 0.43 0.33 4.61 1.17 0.45 0.34

TABLE XVII Energy Cyan Magenta Yellow Cross- Supplied printed printedprinted Talk (J/cm²) density density density M/Y Yellow 3.07 0.11 0.130.20 0.65 3.40 0.10 0.13 0.20 0.65 3.74 0.10 0.13 0.20 0.65 4.08 0.100.14 0.22 0.64 4.42 0.10 0.16 0.22 0.73 4.75 0.10 0.21 0.24 0.88 5.090.11 0.33 0.27 1.22 0.18 5.43 0.11 0.53 0.31 1.71 0.11 5.77 0.13 0.800.38 2.10 0.10 6.10 0.14 0.97 0.43 2.25 0.10 6.45 0.14 1.02 0.45 2.270.11

TABLE XVIII Energy Cyan Magenta Yellow Cross- Supplied printed printedprinted Talk (J/cm²) density density density Y/M Magenta 1.82 0.11 0.130.20 1.53 2.07 0.11 0.13 0.22 1.69 2.33 0.11 0.13 0.27 2.08 2.58 0.100.13 0.31 2.38 2.84 0.11 0.14 0.36 2.57 3.09 0.10 0.15 0.48 3.20 3.350.11 0.17 0.59 3.47 0.00 3.60 0.11 0.19 0.71 3.74 0.01 3.86 0.11 0.200.76 3.80 0.02 4.11 0.11 0.21 0.88 4.19 0.01 4.37 0.11 0.21 0.84 4.000.02

The results obtained by writing on combinations of two color layers areshown in Tables XIX, XX and XXI. Table XIX illustrates the result ofprinting simultaneously on the yellow and magenta layers with a singlethermal print head. The resulting print is red in color. Table XX showsthe result of printing simultaneously on the cyan and yellow layers,giving a green print, and Table XXI shows the result of printing on thecyan and magenta layers to give a blue print.

TABLE XIX Energy Cyan Magenta Yellow Supplied printed printed printed(J/cm²) density density density 4.89 0.10 0.12 0.20 5.47 0.11 0.14 0.236.08 0.11 0.17 0.28 6.66 0.11 0.27 0.38 7.26 0.12 0.40 0.50 7.84 0.130.80 0.65 8.45 0.15 1.20 0.84 9.03 0.18 1.60 1.11 9.63 0.19 1.71 1.2610.21 0.19 1.69 1.39 10.82 0.20 1.62 1.42

TABLE XX Energy Cyan Magenta Yellow Supplied printed printed printed(J/cm²) density density density 3.61 0.11 0.13 0.20 4.14 0.11 0.13 0.204.69 0.12 0.13 0.22 5.21 0.13 0.14 0.27 5.76 0.17 0.15 0.32 6.29 0.310.19 0.43 6.84 0.46 0.26 0.55 7.36 0.67 0.33 0.57 7.91 0.92 0.43 0.678.44 1.23 0.54 0.84 8.99 1.36 0.58 0.93

TABLE XXI Energy Cyan Magenta Yellow Supplied printed printed printed(J/cm²) density density density 4.86 0.11 0.12 0.19 5.47 0.11 0.13 0.246.10 0.12 0.13 0.20 6.71 0.13 0.15 0.21 7.34 0.15 0.17 0.22 7.95 0.320.26 0.25 8.58 0.51 0.42 0.31 9.19 0.69 0.76 0.39 9.82 0.88 1.01 0.4710.43 1.40 1.27 0.59 11.06 1.49 1.31 0.61

Table XXII presents the color densities resulting from printing on allthree color layers in a single pass. The resulting print is black.

TABLE XXII Energy Cyan Magenta Yellow Supplied printed printed printed(J/cm²) density density density 6.68 0.11 0.13 0.20 7.54 0.11 0.14 0.248.43 0.11 0.17 0.29 9.29 0.11 0.23 0.37 10.18 0.18 0.43 0.43 11.04 0.290.81 0.71 11.93 0.41 1.21 0.94 12.79 0.64 1.59 1.12 13.68 0.89 1.81 1.3814.54 1.17 1.79 1.46 15.43 1.29 1.71 1.55

A preferred embodiment of a method similar to that illustrated in FIG.14, but adapted for addressing three different color-forming layers ofan imaging member similar to that illustrated in FIG. 9, will now bedescribed in more detail.

Referring now to FIG. 19, there is seen a thermal imaging member 190that includes a substrate 197, that can be transparent, absorptive, orreflective; three color-forming layers 196, 194, and 192, that may becyan, magenta and yellow, respectively; spacer layers 195 and 193; andan overcoat layer 191.

Each color-forming layer changes color, e.g., from initially colorlessto colored, when heated to a particular temperature referred to hereinas its activating temperature.

Any color order of the color-forming layers can be chosen. One preferredcolor order is as described above. Another preferred color order is onein which the three color-forming layers 196, 194, and 192 are yellow,magenta and cyan, respectively.

The function of the spacer layers is control of thermal diffusion withinthe imaging member 190. Spacer layer 193 is preferably thinner thanspacer layer 195, provided that the materials comprising both layershave substantially the same thermal diffusivity. Preferably, spacerlayer 195 is at least four times thicker than spacer layer 193.

Although six layers are shown disposed on the substrate in FIG. 19,additional barrier layers may be incorporated into the thermal imagingmember 190, for example to protect the image from atmospheric oxygen,ultraviolet radiation, etc. The presence or absence of such layers doesnot affect the methods or devices of the present invention. An exampleof a preferred thermal imaging member of the present invention isdescribed in U.S. patent application Ser. No. 11/400,735.

All the layers disposed on the substrate 197 are substantiallytransparent before color formation. When the substrate 197 is reflective(e.g., white), the colored image formed on imaging member 190 is viewedthrough the overcoat 191 against the reflecting background provided bythe substrate 197. The transparency of the layers disposed on thesubstrate ensures that the colors printed in each of the color-forminglayers may be viewed in combination.

Referring now to FIG. 20, there is seen a schematic, cross-sectionalview of a typical thermal printing arrangement in which a thermalprinting head 200 and thermal imaging member 190 of the presentinvention are held in intimate contact by a platen 208 (that may be aroller (as shown) or a nonrotating element) that biases the thermalimaging member 190 against thermal printing head 200. As shown in FIG.20, a typical thermal printing head comprises a support 204 that carriesboth the driving circuitry 205 and the assembly comprising the heatingelements. The heating elements 207 are carried by a glaze layer 202 incontact with a ceramic substrate 201, and covered by a thin,thermally-conductive overcoat (not shown). Ceramic substrate 201 is incontact with support 204. Shown in the figure is an optional raised“glaze bump” 203 on which the heating elements 207 are located. Theheating elements may be carried by the surface of glaze layer 202 whenglaze bump 203 is absent. Wires 206 provide electrical contact betweenthe heating elements 207 and the driving circuitry 205 through patternedconductive connections 212. Heating elements 207 are in contact with theovercoat layer 191 of imaging member 190 through the thin,thermally-conductive overcoat layer.

In the arrangement of FIG. 20, therefore, control of the amplitude andduration of the electrical power supplied to the heating elements 207controls the temperature evolution of the surface of imaging member 190that carries the overcoat 191. In a preferred embodiment of the presentinvention, thermal printing head 200 is held fixed relative to thechassis of the printer while imaging member 190 is transported past theheating elements 207. The transport of the thermal imaging member may beby means of drive rollers (not shown), by driven rotation of the platen208, or by other transport means that are known in the art. During asingle pass of the imaging member 190 past the heating elements, precisecontrol of the amplitude and duration of the power supplied to theheating elements allows any combination of colors to be formed in thethree color-forming layers 192, 194 and 196. In other words, afull-color image may be printed in a single pass of imaging member 190beneath thermal printing head 200.

FIG. 21 shows schematically the line of heating elements 207 of thethermal printing head 200 in plan view. Four individual heating elements210 a-210 d are shown, each of which is a resistor that is connected toa power supply and to a ground by connections 212. As discussed above,in a typical thermal printing head there may be 150-600 such heatingelements per inch. In some embodiments, a single heating elementcorresponds to a single pixel of an image; in other embodiments pairs orother combinations of heating elements may correspond to a single pixel.In the discussion that follows it is assumed that a single heatingelement corresponds to a single pixel in one row of pixels of an image,and that columns of pixels are rendered by translation of the imagingmember past the row of heating elements.

As discussed above with reference to FIG. 14, and discussed in detail incopending U.S. patent application Ser. No. 11/159,880, electronicpulsing techniques have been designed that allow control of thetemperature of the surface of imaging member 190 without requiringmodulation of the voltage of the electrical power supplied to theheating elements. This is achieved by providing many short pulses, at aconstant voltage, with a frequency high enough that, given the timeconstant of the thermal printing head, the pulses are not individuallyresolved as printed dots in the thermal imaging member 190. Changing theduty cycle of these pulses changes the average power supplied to theheating element and thereby controls the temperature achieved at the topsurface of the imaging member.

FIG. 14 illustrates the case of printing in a single pass using twodifferent average power levels to address two different color-forminglayers in a thermal imaging member. As used herein, the phrase “addressa color-forming layer” means “heat a color-forming layer to atemperature above the activating temperature for that layer”. Whenaddressing three different color-forming layers, such as are provided inimaging member 190, three different average power levels must besupplied.

In a preferred printing method of the present invention, the time forprinting each line (i.e., row) of an image is divided into manysubintervals. For example, referring to FIG. 22, a graph 220 is shownthat plots the voltage across a single print head element (such as anyone of print head elements 210 a-d) over time. Line interval 224 issubdivided into a plurality of subintervals 226. In each of thesubintervals, each print head heating element (also referred to hereinsimply as a “print head element”) potentially receives an electricalpulse. In the particular example illustrated in FIG. 22, pulses 222 areprovided in the first three of subintervals 226.

Furthermore, the line printing time can be divided into three segments,each containing a portion of the subintervals, as shown by the graph 230in FIG. 23. Line interval 234 is divided into three segments 238 a, 238b and 238 c. The first segment 238 a includes subintervals 236 a; thesecond segment includes subintervals 236 b; and the third segmentincludes subintervals 236 c. The pulses 232 a in the first segment 238 aare given a larger pulse duty cycle (the pulse duty cycle being thefraction of a subinterval during which power is applied) than the pulses232 b in the second segment 238 b, which in turn are given a largerpulse duty cycle than the pulses 232 c in the third segment 238 c. Thepulse duty cycle determines the average power being applied to the printhead element during the segment and is used to select a particular oneof the color-forming layers in the thermal imaging member 190, andtherefore to select a particular color to print.

In the example illustrated in FIG. 23, the average power supplied insegment 238 a is higher than that in segment 238 b, which in turn ishigher than that in segment 238 c. Conversely, the duration of segment238 a is shorter than the duration of segment 238 b, which is shorterthan the duration of segment 238 c. The pulses supplied in segment 238 aare therefore used to form color in the color-forming layer requiringthe highest activating temperature and the shortest heating time (i.e.,color-forming layer 192 in FIG. 19); the pulses supplied in segment 238b are used to form color in the color-forming layer requiring theintermediate activating temperature and the intermediate heating time(i.e., color-forming layer 194 in FIG. 19) and the pulses supplied insegment 238 c are used to form color in the color-forming layerrequiring the lowest activating temperature and the longest heating time(i.e., color-forming layer 196 in FIG. 19). The colors requiring high,intermediate, and low activating temperatures are hereinafter referredto as colors A, B and C, respectively.

When printing a continuous series of lines in an image, there are twopossible permutations of the temporal color order: ABCABCABC . . . etc.,and cyclic permutations thereof, and ACBACBACB . . . etc., and cyclicpermutations thereof, when the same color order is used for every linein the image. Either permutation may be used in the practice of thepresent invention, but the permutation ABCABCABC . . . etc., and cyclicpermutations thereof, is particularly preferred. It is not, however,necessary for the practice of the present invention that the same colororder be used for every line of the image, or for every pixel in a givenline of the image.

In some instances the method described above for controlling the printhead may not be completely satisfactory. For example, a conventionalthermal print head typically has one or a small number of “strobe”signal(s) that service(s) all print head elements in the print head. Thestrobe signal determines the pulse duty cycle, and as a consequence allor a significant fraction of the print head elements 210 a-d in printhead 200 have the same pulse duty cycle in each subinterval. The pulseduty cycle, in turn, determines the color-forming layer being printed,as described above, and therefore it follows that during eachsubinterval all or a significant fraction of heating elements 210 a-dare printing on the same color-forming layer of the thermal imagingmember 190. Therefore, at any moment in time all or a significantfraction of the heating elements 210 a-d are printing the same color.This condition precludes the use of screening patterns that call forsome of the heating elements 210 a-d to be addressing one color-forminglayer (and therefore printing one color) while other ones of the heatingelements 210 a-d are addressing another color-forming layer (andtherefore printing another color).

Note further that power is typically provided simultaneously to multipleprint head elements in a print head. Ordinarily, the printer powersupply is chosen to satisfy the “worst case” demand represented by thesupply of power to all of the print head elements simultaneously. Thistypically results in the choice of a larger and more expensive powersupply than would be required to fulfill the “average” power demand.Power supplies may be chosen to satisfy this peak power requirement evenwhen the average power provided to the print head elements is low, as isthe case, for example, when there are repeated segments with lowduty-cycle printing. What is further needed, therefore, are improvedtechniques for performing screening in a printer to reduce the peakpower requirements.

In one aspect of the invention there is disclosed a multicolor thermalimaging system wherein different heating elements on a thermal printhead can address different color-forming layers of a multicolor thermalimaging member simultaneously. The line-printing time is divided intosegments, each of which is divided into a plurality of subintervals. Allof the pulses within the segments have the same energy. In oneembodiment, every pulse has the same amplitude and duration. Differentcolors are selected for printing during the different segments byvarying the fraction of subintervals that contain pulses. This techniqueallows multiple colors to be printed using the same strobe pulses.Pulsing patterns may be chosen to reduce the coincidence of pulsesprovided to multiple print head elements, thereby reducing the peakpower requirements of the print head.

In a typical embodiment of the present invention, the thermal imagingmember is translated at a speed of 0.1 inch/second relative to thethermal printing head, and the image resolution in the transportdirection is 600 dots per inch (dpi). The time taken to print one lineis therefore about 16.7 milliseconds (msec). The rate at which pulsesare provided to a single heating element by the controlling circuitry ofthe thermal printing head (shown as 205 in FIG. 20) is about 1 pulse per10 microseconds (μsec). Therefore, about 1670 pulses can be providedduring the time taken to print a single line of the image. Rather thanadjust the duty cycle at the level of the individual pulses, it ispossible to adjust the average power provided in three segments of thetime taken to print a line by a choice of spacing between the pulses ineach segment, each pulse having the same duty cycle.

For example, referring to FIG. 24, a graph 240 is shown that plots thevoltage across a single print head element over time according to oneembodiment of the present invention. Line interval 244 is divided intothree segments 248 a, 248 b and 248 c, that are used to print colors A,B and C, respectively. Each of the segments 248 a-c is furthersubdivided into an on-time and an off-time. More specifically, segment248 a is divided into on-time 241 a and off-time 243 a, segment 248 b isdivided into on-time 241 b and off-time 243 b, and segment 248 c isdivided into on-time 241 c and off-time 243 c. No pulses are provided inthe off-time of a segment. Pulses may be provided during the on-time ofa segment. Although in the example illustrated in FIG. 24, each of thesegments 248 a-c contains a single on-time followed by a singleoff-time, this is not a requirement of the present invention. Segmentsmay include other numbers of on-times and off-times arranged in ordersother than that shown in FIG. 24.

Each of the on-times 241 a-c is an example of a “portion” of the lineinterval 244, as that term is used herein. Note that a segment need notinclude an off-time. In other words, the on-time of a segment may be theentire segment, in which case the term “portion” also refers to theentire segment. Likewise, a given segment need not include an on-time.The relative sizes of on-time and off-time portions within a segment aredetermined by the density of the color that is intended to be printed. Asegment may include multiple portions, alternating between on-time andoff-time portions.

Line interval 244 includes pulses 242, all of which have the sameenergy. In the particular example illustrated in FIG. 24, all of thepulses 242 have the same amplitude and duration, although this is notrequired. Note further that the amplitude of all of the pulses 242 isthe maximum (100%) voltage V_(bus). Note, however, that this is not arequirement of the present invention.

Segment 248 a is divided into subintervals 246 a. Pulses 242 a havingthe same energy are provided in on-time portion 241 a of the firstsegment 248 a. Although in the particular example illustrated in FIG.24, pulses are provided in all of the subintervals 246 a in the on-timeportion 241 a of segment 248 a, this is not required. Rather, pulses maybe provided in fewer than all of the subintervals 246 a in the on-timeportion 241 a, and in any pattern. In one particular pattern, pulses maybe provided in one out of every N_(A) subintervals 246 a of portion 241a of segment 248 a. In general, the pulsing pattern, the voltageV_(bus), and the duration of the pulses 242 a may be chosen so that theaverage power in the first on-time portion 241 a selects a first one ofthe color-forming layers in the thermal imaging member 190 for printing(resulting in formation of color A).

Segment 248 b is divided into subintervals 246 b. In one preferredarrangement, subintervals 246 b are the same length as subintervals 246a, and pulses may be provided in one out of every N_(B) subintervals 246b of portion 241 b of segment 248 b. In the particular exampleillustrated in FIG. 24, pulses 242 b having the same energy are providedperiodically in only one out of every three of the subintervals 246 b inportion 241 b. In the remaining subintervals in portion 241 b no pulsesare provided. In general, the pulsing pattern, the voltage V_(bus), andthe duration of the pulses 242 b may be chosen so that the average powerin the on-time portion 241 b selects a second one of the color-forminglayers in the thermal imaging member 190 for printing (resulting information of color B). Note that although pulses are shown in FIG. 24 asprovided periodically in portion 241 b, this is not required. Rather,pulses may be provided in any suitable pattern in portion 241 b, asdescribed in more detail in U.S. patent application Ser. No. 11/159,880.

Finally, segment 248 c is divided into subintervals 246 c. In oneparticular pattern, subintervals 246 c are the same length assubintervals 246 a and 246 b, and pulses may be provided in one out ofevery N_(C) subintervals 246 c of portion 241 c of segment 248 c. In theparticular example illustrated in FIG. 24, pulses 242 c having the sameenergy are provided periodically in only one out of every eight of thesubintervals 246 c in portion 241 c. In the remaining subintervals inportion 241 c no pulses are provided. In general, the pulsing pattern,the voltage V_(bus), and the duration of the pulses 242 c may be chosenso that the average power in the on-time portion 241 c selects a thirdone of the color-forming layers in the thermal imaging member 190 forprinting (resulting in formation of color C). As was the case forportion 241 b, described above, although pulses are shown in FIG. 24 asprovided periodically in portion 241 c, this is not required.

Although in the example illustrated in FIG. 24 the on-time portions 241a, 241 b and 241 c occupy the leading subintervals 246 a, 246 b and 246c of the segments 248 a, 248 b and 248 c, respectively, this is notrequired as described in more detail below.

Since the thermal time constant of the print head is typically muchlonger than the length of one of the subintervals 246 a-c, the averagepower in portion 241 b of the second segment 248 b is approximatelyN_(A)/N_(B) times the average power in portion 241 a of the firstsegment 248 a, and the average power in portion 241 c of the thirdsegment 248 c is approximately N_(A)/N_(C) times the average power inportion 241 a of the first segment 248 a. In other words, the averagepower in the portions 241 b and 241 c is reduced not by varying theduration of individual pulses but by selecting the fraction ofsubintervals in which the print head element is pulsed.

Note that the scheme described above with respect to FIG. 24 still uses“duty cycle” as the means of modulating the power provided to the printhead. The scheme illustrated by FIG. 24, however, modulates duty cycleat a coarser level than techniques that modulate duty cycle at the levelof individual pulses. More specifically, the scheme illustrated in FIG.24 modulates duty cycle by adjusting the fraction of pulses that areprovided during a segment portion, rather than by adjusting the pulseduty cycle of individual pulses. This difference allows the same pulseduration to be used in all of the segments 248 a-c, and thereforeenables the same strobe pulse to be used in all of the segments 248 a-c(and therefore to be used to print multiple colors).

Referring to FIG. 25, a flowchart is shown of a method 250 that isperformed by the printer in one embodiment of the present invention toapply the techniques described above with reference to FIG. 24 whenproducing output on the thermal imaging member 190. Those havingordinary skill in the art will appreciate how to implement the method250 as part of a method for printing a digital image on the thermalimaging member 190.

The method 250 identifies a common energy for all pulses (step 251).Recall, for example, that the pulses 242 a-c in FIG. 24 all have thesame energy.

The method 250 enters a loop over each segment S in a line interval(step 252). For example, referring again to FIG. 24, the first segmentmay be segment 248 a, the second segment may be segment 248 b, and thethird segment may be 248 c. The method 250 identifies the color-forminglayer of the thermal imaging member 190, corresponding to the segment S,which is to be addressed (step 253).

The method 250 identifies an average power P_(AVG) to be provided to acorresponding print head element during segment S to address thecolor-forming layer identified in step 253 (step 254). Identification ofan average power may be achieved by a lookup of values obtained byprevious experiments. Such experiments may be carried out, for example,by providing a representative thermal imaging member 190 and testing theoutput obtained by printing at various different average power levels.

The method 250 identifies a pattern of pulses that produces(approximately) the average power P_(AVG), subject to the constraintthat each of the pulses has the common energy identified in step 251(step 255). Note that any pattern satisfying the specified constraintsmay be selected in step 255. The pulse pattern may be a pattern thatonly occupies subintervals in a designated “on-time” portion of asegment, such as on-time portions 241 a-c in FIG. 24. The pulse patternidentified in step 255 may occupy all of the subintervals in thecorresponding segment portion (as in the case of the pulses 242 a insegment portion 241 a) or fewer than all of the subintervals in thecorresponding segment portion (as in the case of the pulses 242 b-c insegment portions 241 b-c). Those having ordinary skill in the art willappreciate that other kinds of patterns may also satisfy the specifiedconstraints.

Since the required average power P_(AVG) varies from color-forming layerto color-forming layer, the pulse pattern selected in step 255 for afirst color-forming layer will differ from the pulse pattern selected instep 255 for a second or a third color-forming layer, as a result of theconstraint that pulses in the patterns have the same energy. Inparticular, such pulse patterns will differ in the fraction ofsubintervals that contain pulses, as illustrated by the example in FIG.24.

The method 250 provides the identified pulse pattern to thecorresponding print head element to select the color-forming layeridentified in step 253 and therefore to print the appropriate color(step 256). The method 250 repeats steps 251-256 for the remainingsegment(s) in the line interval (step 257).

Note that the pulsing pattern for each segment may either remainconstant or change from line time to line time, and/or from print headelement to print head element, within a single line time.

It should be appreciated, in accordance with the teachings above, thateach of the segments 248 a-c may correspond to a different color to beprinted. In a preferred example, the pulses 242 a provided in the firstsegment 248 a may be used to address a yellow color-forming layer of thethermal imaging member 190; the pulses 242 b provided in the secondsegment 248 b may be used to address a magenta color-forming layer ofthe same thermal imaging member 190; and the pulses 242 c provided inthe third segment 248 c may be used to address a cyan color-forminglayer of the same thermal imaging member 190.

In the example illustrated in FIG. 24, pulses 242 b and 242 c are issuedregularly in one out of every N_(B) and one out of every N_(C) of thesubintervals 246 b-c, respectively. These are special cases of what isreferred to herein as “1-out-of-N” pulsing, in which N=N_(B) or N_(C).In the case of N=1, pulses are provided in every subinterval and themaximum average power P_(MAX) is obtained.

It may appear to be a limitation of the techniques disclosed above that1-out-of-N pulsing does not allow the selection of an arbitrary valuefor the average power. That is to say, 1-out-of-2 pulsing reduces theaverage power by 2 (i.e., to P_(MAX)/2), 1-out-of-3 pulsing reduces theaverage power by 3 (i.e., P_(MAX)/3), and in general 1-out-of-N pulsingreduces power by N (i.e., to P_(MAX)/N). Solely using 1-out-of-Npulsing, therefore, does not allow for reduction of average power tovalues other than P_(MAX)/N for single integral values of N. If fineradjustment is desired, it may be obtained using any of a variety oftechniques involving the issuance of more irregular pulse streams, whichare described in detail in U.S. patent application Ser. No. 11/159,880.

For typical applications, pulsing in every subinterval in first segmentportion 241 a of FIG. 24 will produce satisfactory results when formingan image in color-forming layer 192 of thermal imaging member 190;pulsing one out of every N_(B) subintervals in the second segmentportion 241 b will produce satisfactory results when forming an image incolor-forming layer 194 of thermal imaging member 190, where N_(B)ranges from 2 to 10, and pulsing one out of every N_(C) subintervals inthe third segment portion 248 c will produce satisfactory results whenforming an image in color-forming layer 196 of thermal imaging member190, where N_(C) ranges from 5 to 40. Especially preferred values ofN_(A), N_(B) and N_(C) are 1, 6-12, and 15-25, respectively.

The amounts of energy E_(A), E_(B) and E_(C) that must be supplied toprint equal densities of colors A, B and C using the method of thepresent invention are not equal, such that E_(A)<E_(B)<E_(C). Therefore,the number of pulses that must potentially be supplied in segment 248 ais less than the number that must be potentially supplied in segment 248b, which is turn is less than the number that must potentially besupplied in segment 248 c. For example, although this is not intended tolimit the invention in any way, the ratio of energies required to reachequal densities in colors A, B, and C may be about 1:1.6:2.2.

A typical allocation of subintervals to segments 248 a-c when the ratioof energies is as described above is: 35 subintervals in segment 248 awith N_(A)=1; 432 subintervals in segment 248 b with N_(B)=8; and 1200subintervals in segment 248 c with N_(C)=16. The maximum number ofpulses 242 a is 35; the maximum number of pulses 242 b is 54 (=432/8),and maximum number of pulses 242 c is 75 (=1200/16), in this example.The proportion of the line time 244 taken up by segment 248 a is 2.1%(=N_(A)*E_(A)(N_(A)*E_(A)+N_(B)*E_(B)+N_(C)*E_(C))); the proportion ofthe line time 244 taken up by segment 248 b is 26%(=N_(B)*E_(B)/(N_(A)*E_(A)+N_(B)*E_(B)+N_(C)*E_(C))); and the proportionof the line time 244 taken up by segment 248 c is 72%(=N_(C)*E_(C)/(N_(A)*E_(A)+N_(B)*E_(B)+N_(C)*E_(C))). The total numberof subintervals used per line interval in this example is 1667(=35+54*8+75*16). Note that this example is given for illustrativepurposes only and is not intended to limit the invention in any way. Theexact allocation of subintervals to each printing segment will varyaccording to the thermal printing head and thermal imaging member used,and will also depend upon other variables including the baselinetemperature, as described in U.S. patent application Ser. No.11/400,735.

Several refinements may be applied to the basic method outlined in FIGS.24 and 25. The time required to print one line (row) of an image is thesame for every heating element of the thermal printing head (e.g.,elements 210 a-d in the line of heating elements 207). Therefore,referring to FIG. 24, line interval 244 is the same for every heatingelement in the printing head. It is not necessary, however, that theproportion of line interval 244 that is taken up by each of segments 248a, 248 b and 248 c be the same for every heating element. Rather thanallocating a fixed proportion of line interval 244 to the three segmentscorresponding to the printing of the three primary colors, segmentallocation can be made dependent on the image content that is intendedto be printed.

This may be illustrated for the case where segment 248 a corresponds tothe printing of yellow, 248 b to the printing of magenta, and 248 c tothe printing of cyan. In certain regions of the image a low density ofmagenta may be combined with a high density of cyan. More time can bemade available for the printing of cyan if, rather than allocating aportion 243 b of segment 248 b to “off-time” magenta, it is madeavailable for the printing of cyan instead.

It is possible to provide dynamic segment allocation to the printing ofall three colors by eliminating the “off-time” portions 243 a-c in eachof segments 248 a-c. There are reasons, however, to provide a fixedallocation of subintervals to segment 248 a (i.e., the segment thatcorresponds to the printing of color A). As noted above, everysubinterval in segment 248 a is available for pulsing. The proportion ofthe line interval that is allocated to segment 248 a is therefore small;in practice, about 5% or less. Thus there is little advantage to begained by using the “off-time” portion of segment 248 a for the printingof another color. As described in more detail below, however, there maybe disadvantages to reallocating the “off-time” portion of segment 248 awhen varying temporal offsets are applied to the overall line intervals244 of individual pixels in a given line of an image in order tominimize the peak power drawn by the thermal printing head (i.e., whenload leveling is attempted).

In the examples described above, the average power provided to a printhead element is varied by varying the pattern of fixed-duration pulsesprovided to a particular print head element. As will now be described inmore detail, in one embodiment of the present invention pulse patternsare provided to a plurality of print head elements in a manner whichreduces the peak power requirements of the print head.

As background, consider, for example, the case in which the pulsingtechniques described above with reference to FIG. 24 are applied to allof the heating elements of the thermal printing head simultaneously.When pulses are applied in portion 241 a of segment 248 a to eachheating element, as would be the case when printing a high density ofcolor A, the total power supplied to the printing head is L*P_(MAX),where L is the number of pixels in a line and P_(MAX) is, as definedabove, the maximum power supplied to the thermal printing head whenprinting a single pixel. The average power supplied to a particularheating element while printing a single line is, however, much less thanP_(MAX). By offsetting the timing of portions 241 a of segments 248 afor individual heating elements with respect to one another it ispossible to reduce the peak power that must be supplied to the thermalprinting head.

In one embodiment of the present invention, therefore, the required sizeof the power supply is reduced by distributing power more evenly overthe line-printing interval to decrease peak power consumption. The powermay be distributed more evenly over the line-printing interval byvarying the pulse sequences that are applied to the print head elementsso as to reduce the sum of the pulse signals applied to the print headelements at any point in time.

In one embodiment of the present invention, the pulse sequences arevaried using time offsets, but without otherwise varying the pulsepatterns. Various methods for achieving this are described in detail inU.S. patent application Ser. No. 11/159,880. One preferred method of thepresent invention, referred to hereinafter as the “pixel column offset”method, is shown in FIG. 26.

Referring now to FIG. 26, there is seen a diagram 260 that shows thetemporal duration and offsets of segments 268 a-c (corresponding tosegments 248 a-c in FIG. 24 and used for addressing colors A, B and C,respectively) for four successive print head elements of the thermalprinting head while printing pixels in the same line (row) of an image.Each print head element addresses a pixel in a line (row) of an imageover a line printing interval of constant duration 264, but the lineprinting intervals of successive pixels are displaced by a time offset269. Since successive pixels printed by a given heating element comprisea column of pixels in the image, time offset 269 leads to a spatialoffset of a whole column of printed pixels.

Also shown in FIG. 26 are on-time portions 261 a-c and off-time portions263 a-c of segments 268 a-c. The image being printed has constantdensity in color C, but a left-to-right gradient in density from high tolow in colors A and B.

Load leveling is achieved by choosing time offset 269 to be the durationT of line printing interval 264 divided by L, the number of pixels in aline (row) of the image. In practice, the time offset must be anintegral number of subintervals, so in one embodiment of the presentinvention the offset for the nth heating element in a line is chosen tobe a number, Z, of subintervals where Z is the nearest integral value of(n*T)/(T_(S)*L), where T_(S) is the duration of one subinterval. Byfollowing this procedure, each line will contain pixels that areapproximately evenly spaced in delay from 0 to T, and the instantaneouspower will be an average of power drawn at evenly spaced moments in theline time. The instantaneous power will therefore be close to theaverage power and the power will be level over the line time. A minorartifact of the procedure is that a printed line that is intended to beperpendicular to the direction of transport of the thermal imagingmember 190 will actually be inclined very slightly to the perpendicular(by the length of one pixel across the width of the image). In practice,this distortion is too small to be readily noticed.

Using the pixel column offset method, the potential locations of pulsesin a given line interval are offset between neighboring pixels in thesame way, independent of image content, provided that the same patternof locations of potential pulses is maintained for every print headelement. Unfortunately, when dynamic segment allocation is applied tothe printing of all three colors by eliminating the “off-time” portions243 a-c in each of segments 248 a-c in FIG. 24, the same pattern oflocations of potential pulses is not necessarily maintained for everyprint head element.

FIG. 27 shows an illustration of the difficulties that may beencountered when combining dynamic segment allocation with pixel columnoffset. In FIG. 27 there is seen a diagram 270 that shows the temporalduration and offsets of segments 278 a-c (corresponding to segments 248a-c in FIG. 24 and used for addressing colors A, B and C, respectively)for four successive print head elements while printing pixels in thesame line (row) of an image. As in FIG. 26, each print head elementaddresses a pixel in a line (row) of an image over a line interval ofconstant duration 274, and successive line intervals are displaced by atime offset 279. In the chart shown in FIG. 27 the number ofsubintervals allotted to segments 278 a and 278 b is shown as havingbeen adjusted by removing the “off-time” portions corresponding toportions 243 a and 243 b in FIG. 24 when printing a left-to-rightdensity gradient across a line (row) from high to low in colors A and B.The unfortunate result of this off-time reallocation is that the evenlyspaced offsets 279 in the pixel column offset method become uneven andthe pixel columns are no longer reliably offset in a manner favorable toload leveling.

This problem can be partially alleviated if the number of subintervalsallotted to segment 278 a is kept constant. Even when a fixed allocationof subintervals is provided for segments 278 a, however, problems mayarise with non-deterministic offsets of pulses in segment 278 c when“off-time” portions of segment 278 b are eliminated. One method of thepresent invention by which this situation may be remedied is to providea variable offset preceding or following segment 278 a, this offsetbeing the remainder when the number of “off-time” subintervals insegment 278 b, Y say, is divided by N_(C) (i.e., Y (mod N_(C)).

Another possible procedure of the present invention is to advance thepulses of segment 278 c into the unused portion of segment 278 b insteps of size N_(C). This ensures that all pulses of segment 278 cmaintain their load-leveling alignment with respect to neighboringpixels.

This is illustrated in FIG. 28, which shows a fixed allocation ofsubintervals for segment 288 a, and dynamic reallocation of “off-time”portions of segment 288 b. For example, when segments 288 a, 288 b, and288 c correspond to the printing of yellow, magenta, and cyan,respectively, and 1-out-of-N_(C) pulsing is used for the printing ofcyan, the cyan printing segment 288 c can be advanced into the unusedmagenta-printing segment 288 b in steps that are sized as a multiple ofN_(C) subintervals. For each step of N_(C) subintervals, one additionalpulse becomes available for printing of cyan. In this way the density ofcyan that may be rendered can be improved in regions of low magentadensity.

In the preferred embodiment of the present invention illustrated in FIG.28, the line interval 284 for printing a particular pixel is dividedinto t subintervals (not shown, numbered S₁ to S_(t)) of equal duration.These subintervals are grouped into three segments, 288 a-c, foraddressing colors A, B and C, respectively. The number of subintervalsallocated to segments 288 a-c are A, B and C, respectively, where A<B<Cand A+B+C=t. Subintervals S₁ to S_(A) are allocated to segment 288 a;subintervals S_(A+1) to S_(A+B) are allocated to segment 288 b; andsubintervals S_(A+B+1) to S_(t) are allocated to segment 288 c. Insegment 288 a, one out of every N_(A) subintervals may contain a pulse;in segment 288 b, one out of every N_(B) subintervals may contain apulse; and in segment 288 c, one out of every N_(C) subintervals maycontain a pulse, where N_(A)<N_(B)<N_(C). The number of subintervalsassigned to segment 288 a is constant, irrespective of image content.The number of subintervals assigned to segment 288 b is either B or thenumber of subintervals needed to render the required density of thecolor B in the pixel being printed, whichever is less. For example, if Xpulses are required to render the desired density of color B, the numberof subintervals allocated will be X*N_(B) (for 1-out-of-N_(B) pulsing),unless this number is greater than B, in which case B subintervals willbe allocated and the density that is achievable will be less than orequal to the density desired). The remaining subintervals are assignedto segment 288 c in blocks of length N_(C). Since N_(C)>N_(B) there isthe possibility of a residual block of subintervals from segment 288 bwith length less than N_(C) that is not allocated to segment 288 c, andis not available for pulsing. When none of color B is called for,therefore, all the subintervals originally allocated to segment 288 bbecome available for printing color C, except for those in any residualblock of length <N_(C), in addition to those already allocated tosegment 288 c.

Pulses may be allocated to segments 288 a-c incrementing forward fromthe beginning of the segment (hereinafter referred to as “bottom-up”allocation), incrementing bidirectionally from the middle of the segment(hereinafter referred to as “center growth” allocation), or incrementingbackwards from the end of the segment (hereinafter referred to as“top-down” allocation). Other manners in which pulses may be allocatedwill occur to one of ordinary skill in the art.

One particular difficulty that may arise using the pulsing techniquesdescribed above occurs when it is intended to print the colorcorresponding to the highest average power (color A) in conjunction withthe color corresponding to the lowest average power (color C) withoutprinting the color corresponding to the intermediate average power(color B). For example, when color A is yellow and color C is cyan,printing the two together should provide the color green (yellow pluscyan) uncontaminated with magenta (color B). It is possible, however,that a juxtaposition of a high-power printing segment with a low-powerprinting segment might produce a transitional region of intermediatepower.

Referring to FIG. 24, the situation of juxtaposing high- and low-powersegments occurs in the transition from one line to the next, i.e., inthe transition between segment 248 c in one line to segment 248 a of thenext. The situation can also occur in the method illustrated in FIG. 28,in the case where there is no printing of color B and segments 288 a and288 c abut within a single line of the image.

The present inventors have found that unintended thermal power averagingbetween the high-power and the low-power printing segments can beavoided if a gap of at least 0.5 msec and preferably at least 1 msec isprovided between a highest-power printing segment and a lowest-powerprinting segment, as is shown in FIG. 29.

FIG. 29 is a diagram showing four neighboring print head elements usinga preferred method of the present invention for printing the combinationof colors A and C. Because there is none of color B required, dynamicreallocation of subintervals from segment 298 b to 298 c is carried out.However, a temporal gap 295 is inserted between segments 298 a and 298 cin order to prevent unintended thermal power averaging to theintermediate power that would lead to formation of color B. Likewise, atemporal gap 297 is inserted between the end of segment 298 c andsegment 298 a of the following line. As mentioned above, these temporalgaps are preferred to be at least 0.5 msec in duration, and especiallypreferred to be at least 1 msec in duration, but this is for the case inwhich a conventional thermal printing head is used to address a thermalimaging member 190 of the type described herein, and the presentinvention is not limited to these values. As will be clear to one ofordinary skill in the art, changes in the design of thermal printingheads, or the use of other heating modalities such as lasers, etc., mayresult in the need for temporal gaps 295 and 297 having durations thatdiffer from these preferred values.

It is not necessary that the temporal gaps 295 and 297 have a constant,fixed duration. In one preferred embodiment, the duration of temporalgap 295 is made dependent upon the number of pulses applied in segment298 a (i.e., to print color A) in such a way that the duration oftemporal gap 295 is made longer when the number of pulses applied insegment 298 a is greater.

A complementary problem applies when it is intended to print the colorcorresponding to the highest average power (color A) in conjunction withthe color corresponding to the intermediate average power (color B)without printing the color corresponding to the lowest average power(color C). For example, when color A is yellow and color B is magenta,printing the two together should provide the color red (yellow plusmagenta) uncontaminated with cyan (color C). It is possible, however,that in a temporal gap between a high-power printing segment and anintermediate-power printing segment a transitional region might average,thermally, to a low power sufficient to activate unwanted color C.

Referring now to FIG. 24, it is seen that there exists a gap, the“off-time” portion 243 a of segment 248 a, between the high-power pulsesin portion 241 a of segment 248 a and the intermediate-power pulsing inportion 241 b of segment 248 b. Further, as discussed above, eliminationof “off-time” portion 243 a and consequent shortening of segment 248 amay lead to problems in load leveling when using the preferred pixelcolumn offset method.

The solution to the difficulty is to rearrange portions 241 a and 243 awithin segment 248 a so that “off-time”portion 243 a precedes “on-time”portion 241 a (i.e., to use “top-down” pulse allocation). In this way,there exists no gap between portion 241 a of segment 248 a and portion241 b of segment 248 b. This preferred pulse sequence of the presentinvention is illustrated in FIG. 30.

Referring to FIG. 30, a graph 300 is shown that plots the voltage acrossa single print head element over time according to a preferredembodiment of the present invention. Line interval 304 is divided intothree segments 308 a, 308 b and 308 c, that are used to print colors A,B and C, respectively. Each of the segments 308 a-c is furthersubdivided into an on-time and an off-time. Segment 308 a is dividedinto on-time 301 a and off-time 303 a, segment 308 b is divided intoon-time 301 b and off-time 303 b, and segment 308 c is divided intoon-time 301 c and off-time 303 c. When more pulses are demanded insegment 308 a, portion 301 a expands and off-time portion 303 acontracts by the same number of subintervals, in the direction shown byblock arrow 305 a. Similarly, block arrows 305 b and 305 c show howportions 301 b and 301 c expand at the expense of portions 303 b and 303c when more pulsing is called for. As described above, in the embodimentof the present invention illustrated in FIG. 30, segment 308 a has“top-down” pulse loading, whereas segments 308 b and 308 c have“bottom-up” pulse loading.

It is to be understood that although the invention has been describedabove in terms of particular embodiments, the foregoing embodiments areprovided as illustrative only, and do not limit or define the scope ofthe invention. Various other embodiments, including but not limited tothe following, are also within the scope of the claims. For example,elements and components described herein may be further divided intoadditional components or joined together to form fewer components forperforming the same functions.

Note that although in the examples described above, all of theindividual pulse duty cycles are set to a single value which may be upto 100%, the common duty cycle may be lower if required by the printhead specification, or if desired for some other reason.

Note that although a particular printer having a single print head and aparticular number of print head elements 207 is shown in FIG. 20, thisis merely an example and does not constitute a limitation of the presentinvention. Rather, embodiments of the present invention may be used inconjunction with various kinds of printers having various numbers ofprint heads, print head elements, and other characteristics.

U.S. Pat. No. 6,661,443 to Bybell and Thornton describes a method forproviding the same amount of energy to each active element in a thermalprint head during each subinterval used to print an image irrespectiveof the number of print head elements that are active during eachsubinterval. The desired amount of energy may be provided to a pluralityof print head elements that are active during a print head cycle bydelivering power to the plurality of print head elements for a period oftime whose duration is based in part on the number of active print headelements. The period of time may be a portion of the print head cycle.According to one embodiment of the present invention, the pulse dutycycle is changed from subinterval to subinterval, implementing aso-called “common mode voltage correction” by varying the pulse durationin response to the change in voltage caused by the change in the numberof active print head elements, thereby maintaining a constant energy forall pulses.

The techniques described above may be implemented, for example, inhardware, software, firmware, or any combination thereof. The techniquesdescribed above may be implemented in one or more computer programsexecuting on a programmable computer including a processor, a storagemedium readable by the processor (including, for example, volatile andnon-volatile memory and/or storage elements), at least one input device,and at least one output device. Program code may be applied to inputentered using the input device to perform the functions described and togenerate output. The output may be provided to one or more outputdevices.

For example, the techniques disclosed herein may be implemented in aprinter or other device having components for performing the functionsillustrated by the system 310 in FIG. 31. An image processing unit 311receives raw print data and performs initial image processing, such asdecompression. The process print data are provided to a thermal historycontrol engine 312, which performs thermal history control on the printdata as described, for example, in U.S. patent application Ser. No.10/910,880.

The output of the thermal history control engine 312 is provided to aprint head resistance correction engine 313, which performs correctionson the print data as described, for example, in U.S. patent applicationSer. No. 10/990,672, filed Jan. 10, 2005.

The output of the print head resistance correction engine 313 isprovided to a pulse pattern generator 314, which generates pulses inaccordance with the techniques disclosed herein. The pulses generated bythe pulse pattern generator 314 are provided to a common mode voltagecorrection engine 315, which performs common mode voltage correction onthe pulses as described, for example, in U.S. Pat. No. 6,661,443.

The output of the common mode voltage correction engine 315 is providedthe thermal print head 316 to pulse the print head 316 accordingly.

Each computer program within the scope of the claims below may beimplemented in any programming language, such as assembly language,machine language, a high-level procedural programming language, or anobject-oriented programming language. The programming language may, forexample, be a compiled or interpreted programming language.

Each such computer program may be implemented in a computer programproduct tangibly embodied in a machine-readable storage device forexecution by a computer processor. Method steps of the invention may beperformed by a computer processor executing a program tangibly embodiedon a computer-readable medium to perform functions of the invention byoperating on input and generating output. Suitable processors include,by way of example, both general and special purpose microprocessors.Generally, the processor receives instructions and data from a read-onlymemory and/or a random access memory. Storage devices suitable fortangibly embodying computer program instructions include, for example,all forms of non-volatile memory, such as semiconductor memory devices,including EPROM, EEPROM, and flash memory devices; magnetic disks suchas internal hard disks and removable disks; magneto-optical disks; andCD-ROMs. Any of the foregoing may be supplemented by, or incorporatedin, specially-designed ASICs (application-specific integrated circuits)or FPGAs (Field-Programmable Gate Arrays). A computer can generally alsoreceive programs and data from a storage medium such as an internal disk(not shown) or a removable disk. These elements will also be found in aconventional desktop or workstation computer as well as other computerssuitable for executing computer programs implementing the methodsdescribed herein.

Although the invention has been described in detail with respect tovarious preferred embodiments, it is not intended to be limited thereto,but rather those skilled in the art will recognize that variations andmodifications are possible, which are within the spirit of the inventionand the scope of the appended claims.

1. A method comprising steps of: (A) identifying a first plurality of pulses to be provided to a thermal print head element in a first segment of a first line time, the first plurality of pulses having a first average power, wherein each of the first plurality of pulses has a common predetermined energy; and (B) identifying a second plurality of pulses to be provided to the thermal print head element in a second segment of the first line time, the second plurality of pulses having a second average power that is less than the first average power, wherein each of the second plurality of pulses has the common predetermined energy; and (C) identifying a third plurality of pulses to be provided to the thermal print head element in a third segment of the first line time, the third plurality of pulses having a third average power that is less than the second average power, wherein each of the third plurality of pulses has the common predetermined energy. 2-24. (canceled) 